KR20150070287A

KR20150070287A - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Info

Publication number: KR20150070287A
Application number: KR1020157012503A
Authority: KR
Inventors: 노리토시 미키; 준 하시모토; 고지 도모에; 마사아키 가타야마
Original assignee: 닛산 가가쿠 고교 가부시키 가이샤
Priority date: 2012-10-18
Filing date: 2013-10-18
Publication date: 2015-06-24
Also published as: JP5930237B2; TW201434970A; KR20170102041A; CN104884533B; JPWO2014061778A1; CN104884533A; KR101988082B1; TWI547524B; WO2014061778A1

Abstract

(1) A composition comprising the following components (A), (B) and (C).
Component (A): a solvent represented by the following formula [1].

(In the formula [1], X ¹ represents an alkyl group having 1 to 4 carbon atoms).
Component (B): at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.
(C): Polysiloxane obtained by polycondensation of an alkoxysilane containing any one of specific alkoxysilanes.

Description

TECHNICAL FIELD [0001] The present invention relates to a composition, a liquid crystal alignment treatment agent, a liquid crystal alignment film and a liquid crystal display element,

The present invention relates to a composition used for forming a resin film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film.

A resin film made of an organic material such as a polymer material is widely used as an interlayer insulating film or a protective film in an electronic device because of its ease of formation and insulation performance. Among them, in a liquid crystal display element well known as a display device, a resin film made of an organic material is used as a liquid crystal alignment film.

2. Description of the Related Art In recent years, liquid crystal display devices have been widely put to practical use in liquid crystal televisions on a large screen and in high-precision mobile applications (display portions of digital cameras and cellular phones). As a result, the size of the substrate used in comparison with the conventional one is increased, and the unevenness of the step of the substrate is increased. Even in such a situation, it has been demanded that a liquid crystal alignment film is uniformly coated on a large substrate or step in terms of display characteristics. When a liquid crystal alignment treatment agent of polyamic acid or a solvent-soluble polyimide (also referred to as a resin) is applied to a substrate in the production process of the liquid crystal alignment film, it is industrially carried out by a flexographic printing method or an inkjet coating method It is common. At this time, as the solvent of the liquid crystal alignment treatment agent, N-methyl-2-pyrrolidone (also referred to as NMP) or γ-butyrolactone (γ-BL Ethylene glycol monobutyl ether, which is a low-solubility solvent (also referred to as a poor solvent), and the like are mixed in order to enhance the coating film property of the liquid crystal alignment film (see, for example, Patent Document 1).

Japanese Unexamined Patent Application Publication No. 2-37324

The liquid crystal alignment film is formed by applying a liquid crystal alignment treatment agent to a substrate and then firing the coating film. At that time, for the purpose of raising the coating film property (also referred to as coatability) of the liquid crystal alignment film, that is, for suppressing the generation of pinholes accompanying cratering, it is required to improve the wettability of the liquid crystal alignment treatment agent . This is required in a liquid crystal alignment treatment agent containing a polyimide-based polymer and a polysiloxane as in the liquid crystal alignment treatment agent containing a conventionally used polyimide-based polymer.

The compatibility of a highly polar NMP or γ-BL with a polysiloxane having a high hydrophobicity can be improved by using a polymer solution obtained by dissolving a polyimide-based polymer and a liquid crystal alignment treatment agent obtained by polysiloxane in NMP or γ-BL, When the composition is applied to a substrate, pinholes accompanying cratering are likely to be generated on the liquid crystal alignment film. That is, in a conventional liquid crystal alignment treatment agent comprising a polyimide-based polymer and a polysiloxane, alignment defects accompanying pinholes are apt to occur.

The resin film obtained from a composition containing a polyimide-based polymer and a polysiloxane has a high chemical stability with respect to a resin film obtained from a composition containing no polysiloxane. Therefore, in addition to the liquid crystal alignment film, And a protective film. Also in these films, it is necessary to improve the coating property of the resin film, that is, to suppress the occurrence of pinholes accompanying cratering on the resin film.

Therefore, the present invention aims to provide a composition having the above characteristics. That is, an object of the present invention is to provide a composition capable of suppressing the generation of pinholes accompanying cratering when a resin film is formed in a composition comprising a polyimide-based polymer and a polysiloxane.

Another object of the present invention is to provide a liquid crystal alignment treatment agent capable of suppressing the occurrence of pinholes accompanying cratering when forming a liquid crystal alignment film in the liquid crystal alignment treatment agent using the above-described composition.

It is another object of the present invention to provide a liquid crystal alignment film corresponding to the above-described requirements. That is, it is an object of the present invention to provide a liquid crystal alignment film capable of suppressing alignment defects accompanying pinholes.

Another object of the present invention is to provide a liquid crystal display element provided with a liquid crystal alignment film corresponding to the above-described requirements.

As a result of intensive studies, the present inventors have found that a polyimide precursor obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid component with a solvent having a specific structure, or at least one polymer selected from a polyimide And a composition containing a polysiloxane having a specific structure are very effective for achieving the above object, and have completed the present invention.

That is, the present invention has the following points.

(1) A composition comprising the following components (A), (B) and (C).

Component (A): a solvent represented by the following formula [1].

[Chemical Formula 1]

(In the formula [1], X ¹ represents an alkyl group having 1 to 4 carbon atoms).

Component (B): at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.

(C): Polysiloxane obtained by polycondensation of an alkoxysilane containing any one of alkoxysilanes represented by the following formula [A1], formula [A2] or formula [A3].

(2)

Wherein A ¹ is an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, an organic group having 8 to 35 carbon atoms having a heterocyclic or steroid structure, A ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, represents, a ³ is. However, m + n + p is 4, each represents an alkyl group of a carbon number of 1 ~ 5, m is an integer of 1 or 2, n is an integer of 0 to 2, p represents an integer of 0 to 3 to be).

(3)

Wherein B ¹ represents an organic group having 2 to 12 carbon atoms and having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acryl group, a ureide group or a cinnamoyl group, B ² each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ³ each represent an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, Represents an integer of 0 to 3, provided that m + n + p is 4).

[Chemical Formula 4]

(In the formula [A3], D ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, D ² is an alkyl group having 1 to 5 carbon atoms, and n is an integer of 0 to 3).

(2) The composition according to the above (1), wherein the component (A) is 50 to 100 mass% of the total solvent contained in the composition.

(3) The composition according to the above (1) or (2), wherein the diamine compound having a carboxyl group as the component (B) is a diamine compound having a structure represented by the following formula [2].

[Chemical Formula 5]

(In the formula [2], a represents an integer of 0 to 4).

(4) The composition according to (1) or (2) above, wherein the diamine compound having a carboxyl group as the component (B) is a diamine compound having a structure represented by the following formula (2a).

[Chemical Formula 6]

(In the formula [2a], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

(5) The composition according to the above (3) or (4), wherein the diamine compound having a carboxyl group is contained in an amount of 20 mol% to 100 mol% in the total diamine used in the component (B).

(6) The process according to any one of (1) to (5) above, wherein the diamine component of the component (B) comprises at least one diamine compound selected from the structures represented by the following formula [2b] &Lt; / RTI >

(7)

(In the formula [2b], Y represents a structure represented by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] m represents an integer of 1 to 4).

[Chemical Formula 8]

(Wherein a is an integer of 0 to 4, and Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15) in the formula [2b-2] , -O-, -CH ₂ represents an O-, -COO- or -OCO-, Y ² is a single bond or - (CH ₂₎ _b - represents a (b is an integer of 1 ~ 15), Y ³ is a single _{bond, - (CH 2) c -} (c is an integer from 1 to 15), represents an -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ is a benzene ring, a cyclohexane ring Or a divalent cyclic group selected from a heterocyclic ring or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton, and any hydrogen atom on the cyclic group may be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms , fluorine-containing alkyl group having 1 to 3 carbon atoms and may be substituted with 1-3 fluorine-containing alkoxy group or a fluorine atom, Y ⁵ is a divalent cyclic group selected from benzene ring, a cyclohexane ring or a heterocyclic ring of And any hydrogen atom on these cyclic groups is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluoro-containing alkoxyl group having 1 to 3 carbon atoms, may be, n represents an integer of 0 ~ 4, Y ⁶ is a fluorine-containing alkoxyl group having 1 to 18 alkyl group, having 1 to 18 fluorine-containing alkyl group, having 1 to 18 carbon atoms, an alkoxyl group or a C 1 to 18 of the represents the formula [2b-3] of the, Y ⁷ represents an alkyl group of a carbon number of 8 to 22, formula [2b-4] of, Y ⁸ and Y ⁹ are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, formula [ 2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms.

(7) The composition according to any one of (1) to (6), wherein the tetracarboxylic acid dianhydride component of the component (B) is represented by the following formula [3].

[Chemical Formula 9]

(In the formula [3], Z ¹ is a group of at least one structure selected from the following formulas [3a] to [3j]).

[Chemical formula 10]

(Formula [3a] of, Z ² ~ Z ⁵ represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and also the same or different and wherein [3g], Z ⁶ and Z ⁷ represents a hydrogen atom or a methyl group And may be the same or different from each other).

(8) The positive resist composition as described in the above item (1), wherein the alkoxysilane represented by the formula (A2) of the component (C) is at least one selected from the group consisting of allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, (Trimethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate or 3- (trimethoxysilyl) propyl methacrylate, vinyltriethoxysilane, The composition according to any one of (1) to (7) above, wherein the composition is at least one selected from the group consisting of propyl methacrylate.

(9) The positive resist composition as described in any one of the above items (1) to (4), wherein the alkoxysilane represented by the formula [A2] of the component (C) is at least one member selected from the group consisting of 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl The composition according to any one of (1) to (7) above, which is at least one selected from the group consisting of silyloxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. .

(10) The positive resist composition as described in any of (1) to (9) above, wherein the polysiloxane of the component (C) is a polysiloxane obtained by polycondensation of the alkoxysilane represented by the formula [A1], the formula [A2] ). &Lt; / RTI >

(11) The liquid crystal composition according to the above (1), wherein as the component (D), at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N- The composition according to any one of (10) to (10) above.

(12) The positive resist composition as described in any one of (1) to (7) above, wherein the component (E) is at least one compound selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, (1) above, which contains at least one of ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether. ) To (11).

(13) A resin film obtained from the composition according to any one of (1) to (12).

(14) A liquid crystal alignment treatment agent obtained from the composition according to any one of (1) to (12).

(15) A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to (14) above.

(16) A liquid crystal alignment film obtained by the ink jet method using the liquid crystal alignment treatment agent described in (14) above.

(17) A liquid crystal display element having the liquid crystal alignment film according to (15) or (16) above.

(18) A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound capable of polymerizing by at least one of an active energy ray and a heat between the pair of substrates is arranged The liquid crystal alignment film according to (15) or (16) above, which is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes.

(19) A liquid crystal display element having the liquid crystal alignment film according to (18).

(20) A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes, wherein a liquid crystal alignment film containing a polymerizable group capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, The liquid crystal alignment film according to (15) or (16) above, wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage between the electrodes.

(21) A liquid crystal display element having the liquid crystal alignment film according to (20) above.

A solvent having a specific structure of the present invention, at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component, and a polysiloxane It is possible to suppress the occurrence of pinholes accompanying cratering on the resin coating when coating the substrate.

Further, the liquid crystal alignment treatment agent comprising the composition of the present invention can suppress the occurrence of pinholes accompanying cratering on the liquid crystal alignment film when the substrate is applied. Therefore, the liquid crystal display element having the liquid crystal alignment film thus obtained becomes a liquid crystal display element free from alignment defects.

As a result of intensive studies, the present inventors have obtained the following findings and have completed the present invention.

The present invention relates to a composition containing the following components (A), (B) and (C), a liquid crystal alignment treatment agent, a resin film obtained by using the composition, a liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent, And a liquid crystal display element having the liquid crystal alignment film.

(A): a solvent represented by the following formula [1] (also referred to as a specific solvent);

(11)

Component (B): at least one polymer (also referred to as a specific polymer) selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.

Component (C): A polysiloxane (also referred to as a specific polysiloxane) obtained by polycondensation of an alkoxysilane containing any one of alkoxysilanes represented by the following formula [A1], formula [A2] or formula [A3].

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

The specific solvent of the present invention usually has a lower surface tension as a solvent than a solvent such as NMP or? -BL used in a composition having a polyimide-based polymer. Therefore, the composition using a specific solvent has a high wettability to the substrate. Therefore, generation of pinholes accompanying cratering on the resin coating can be suppressed.

Further, since the composition of the present invention is not a solvent having a high polarity such as NMP or? -BL, even when a polymer solution of a specific polysiloxane or a specific polysiloxane is mixed into a polymer solution prepared by dissolving a specific polymer in a specific solvent, The compatibility of the solvent and the polymer solution of the specific polysiloxane or the specific polysiloxane is improved. Therefore, when this composition is applied to a substrate, generation of pinholes accompanying cratering on the resin coating can be suppressed.

In view of the above, the composition of the present invention can suppress defects such as pinholes caused by cratering on the resin coating when coating the substrate. In addition, the liquid crystal alignment treatment agent obtained from the composition of the present invention can also achieve the above-mentioned effects for the same reason.

Hereinafter, embodiments of the present invention will be described in detail.

The specific solvent as the component (A) of the present invention is a solvent represented by the following formula [1].

[Chemical Formula 15]

Specifically, the structure represented by the following formulas [1-1] to [1-6] is exemplified.

[Chemical Formula 16]

Among them, the formula [1-1] or the formula [1-2] is preferable in view of the boiling point and the availability of the solvent.

The specific solvent of the present invention is preferably 50 to 100% by mass of the entire solvent contained in the composition or the liquid crystal alignment treatment agent using the composition, in order to enhance the effect of increasing the wettability to the above-described substrate. Among these, 55 to 100 mass% is preferable. More preferred is 55 to 95 mass%.

The effect of the present invention, that is, the effect of the present invention, that is, the effect of the present invention, that the coating solution for the substrate has a high wetting property and is excellent in the coating property, A liquid crystal alignment film can be obtained.

&Lt; Specific polymer &

The specific polymer as the component (B) of the present invention is at least one polymer selected from a polyimide precursor or polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group with a tetracarboxylic acid component.

The polyimide precursor has a structure represented by the following formula [A].

[Chemical Formula 17]

(In the formula [A], R ¹ is a tetravalent organic group, R ² is a divalent organic group having a carboxyl group, A ¹ and A ² are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, A ³ and A ^{4 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, which may be the same or different, and n represents a positive integer).

The diamine component is a diamine compound having two primary or secondary amino groups in the molecule, and examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic acid dianhydride, a dicarboxylic acid dihalide compound , A dicarboxylic acid dialkyl ester compound, or a dialkyl ester dihalide compound.

The specific polymer of the present invention can be obtained by relatively easily obtaining a diamine compound having a carboxyl group represented by the following formula [B] and a tetracarboxylic acid dianhydride represented by the following formula [C] D] or a polyimide obtained by imidizing the polyamic acid is preferable.

[Chemical Formula 18]

(In the formulas [B] and [C], R ¹ and R ² have the same meanings as defined in formula [A]).

[Chemical Formula 19]

(In the formula [D], R ¹ and R ² have the same meanings as defined in formula [A]).

In addition, the polymers of the usual synthesis techniques, equation [D] obtained in the above-mentioned formula [A] represented by A ¹ and A carbon number of alkyl group of 1-8 of Figure ^2, and the equation [A] represented by A ³ and A ⁴ An alkyl group having 1 to 5 carbon atoms or an acetyl group may be introduced.

The diamine compound having a carboxyl group of the present invention is a diamine compound having a structure represented by the following formula [2] in the molecule.

[Chemical Formula 20]

In the formula [2], a represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

Specific examples of the diamine compound having a structure represented by the formula [2] include a structure represented by the following formula [2a].

[Chemical Formula 21]

In formula [2a], a represents an integer of 0 to 4. Among them, 0 or 1 is preferable from the viewpoint of availability of raw materials and easiness of synthesis.

In the formula [2a], n represents an integer of 1 to 4. Among them, 1 is preferable from the viewpoint of easiness of synthesis.

The method for producing the diamine compound represented by the formula [2a] of the present invention is not particularly limited, but preferred examples include the following.

As an example, the diamine compound represented by the formula [2a] is obtained by synthesizing a dinitro compound represented by the following formula [2a-A], reducing the nitro group and converting it into an amino group.

[Chemical Formula 22]

(In the formula [2a-A], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2a-A] is not particularly limited, and usually, a palladium- Hydrazine or hydrogen chloride using carbon as a catalyst, platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum sulfide carbon as a catalyst.

Examples of the diamine compound having a carboxyl group of the present invention include structures represented by the following formulas [2a-1] to [2a-4].

(23)

In the formula ^[2a-1], A 1 represents a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, - O-, -CO-, -NH-, -N ( CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH ₃₎ - or -N (CH ₃₎ represents a CO-. Among them, a single bond, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N (CH ₃ ) -, -CONH- , -NHCO-, -COO- or -OCO-. More preferred is a single bond, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -NH- or -N (CH ₃ ) -.

In the formula [2a-1], m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4. In particular, m ¹ + m ² is 1 or 2 are preferred.

In the formula [2a-2], m ³ and m ⁴ each represent an integer of 1 to 5. Among them, 1 or 2 is preferable from the viewpoint of ease of synthesis.

In the formula [2a-3], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a linear alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [2a-3], m ⁵ represents an integer of 1-5. Among them, 1 or 2 is preferable.

In the formula [2a-4], A ³ is a single _{bond, -CH 2 -, -C 2 H} 4 -, -C (CH 3) 2 -, -CF 2 -, -C (CF 3) 2 -, - O-, -CO-, -NH-, -N ( CH 3) -, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 -, -COO-, -OCO-, -CON (CH ₃₎ - or -N (CH ₃₎ represents a CO-. Among them, a single bond, -CH ₂ -, -C (CH ₃ ) ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO-, or -OCO-. More preferred are -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2 - is, -COO- or -OCO-.

In the formula [2a-4], m ⁶ represents an integer of 1 to 4. Among them, 1 is preferable from the viewpoint of easiness of synthesis.

The diamine compound having a carboxyl group of the present invention is preferably 20 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, of the total diamine component.

The diamine compound having a carboxyl group may be one or two kinds depending on the solubility of the specific polymer of the present invention in the solvent, the coating property of the composition, the orientation of the liquid crystal when the liquid crystal alignment film is used, the voltage retention rate, Or more.

&Lt; Second diamine compound >

As the diamine component for producing the specific polymer of the present invention, a diamine compound (also referred to as a second diamine compound) represented by the following formula [2b] may be used as the second diamine compound.

&Lt; EMI ID =

(In the formula [2b], Y represents a structure represented by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] and m represents an integer of 0 to 4).

(25)

In the formula [2b-1], a represents an integer of 0 to 4. Of these, an integer of 0 or 1 is preferable in view of availability of raw materials and ease of synthesis.

Y ¹ is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO-, or -OCO- in the formula [2b-2] . Among them, a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable in view of availability of raw materials and ease of synthesis desirable. More preferred is a single bond, - (CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2b-2], Y ² represents a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or - (CH ₂ ) _b - (b is an integer of 1 to 10) is preferable.

In formula [2b-2], Y ³ represents a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO- . Among them, a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferable from the viewpoint of easiness of synthesis. More preferably a single bond, - (CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In formula [2b-2], Y ⁴ is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁴ may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms and having a steroid skeleton. Among them, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable from the viewpoint of ease of synthesis.

In formula [2b-2], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups may be substituted with an alkyl group having 1 to 3 carbon atoms, , A fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Among them, a benzene ring or a cyclohexane ring is preferable.

In the formula [2b-2], n represents an integer of 0 to 4. Among them, from the viewpoint of availability of raw materials and easiness of synthesis, 0 to 3 is preferable. More preferred is 0 to 2.

In the formula [2b-2], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 18 carbon atoms. Among them, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorinated alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferably an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

Preferable combinations of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2b-2] for constituting the substituent Y in the formula [2b] (2-1) to (2-629) listed in Tables 6 to 47 of Tables 13 to 34 of the Japanese Patent Application Laid-Open No. 2005- 132751 (published on October 27, 2011). In each table of the International Publication, Y ¹ to Y ⁶ in the present invention are represented as Y ¹ to Y ⁶ , while Y ¹ to Y ⁶ are read in Y ¹ to Y ⁶ .

In the formula [2b-3], Y ⁷ represents an alkyl group of a carbon number of 8 to 22.

In the formula [2b-4], Y ⁸ and Y ⁹ each independently represent a hydrocarbon group having 1 to 6 carbon atoms.

In the formula [2b-5], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms.

The method for producing the diamine compound represented by the formula [2b] of the present invention is not particularly limited, but preferable examples include the following.

As an example, the diamine compound represented by the formula [2b] can be obtained by synthesizing a dinitro compound represented by the following formula [2b-A], reducing the nitro group and converting it into an amino group.

(26)

(Wherein Y is at least one selected from the above-mentioned formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] or formula [2b-5] And m represents an integer of 0 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [2b-A] is not particularly limited, and a palladium- Hydrazine or hydrogen chloride using carbon as a catalyst, platinum oxide, Raney nickel, platinum black, rhodium-alumina or platinum sulfide carbon as a catalyst.

Specific structures of the second diamine compound represented by the formula [2b] of the present invention are shown below, but the present invention is not limited to these examples.

Namely, examples of the second diamine represented by the formula [2b] include m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4- 2b-6] to [2b-46] in addition to 5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol and 4,6- And the like.

(27)

(In the formula [2b-6] ~ formula [2b-9], A ¹ is an alkyl group or a fluorine-containing alkyl group having a carbon number of 1 to 22).

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(Wherein R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents a carbon number An alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(40)

(Wherein R ³ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - (CH ₂₎ CH ₂ -, and R ⁴ represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.

(41)

(Formula [2b-40] and formula [2b-41] of, R ⁵ is _{-COO-, -OCO-, -COOCH 2 -,} -CH 2 OCO-, -CH 2 O-, -OCH 2 -, - CH ₂ - or -O-, and R ⁶ is a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

(42)

(Formula [2b-42] and formula [2b-43] of, R ⁷ represents an alkyl group having a carbon number of 3 to 12. In addition, the 1,4-cis-cyclohexylene-trans reason, each trans isomer is preferred) .

(43)

(In the formula [2b-44] and the formula [2b-45], R ⁸ represents an alkyl group having 3 to 12 carbon atoms, and the cis- trans isomer of 1,4-cyclohexylene is preferably a trans isomer) .

(44)

(In the formula [2b-46], B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents a 1,4-cyclohexylene group or a 1,4-phenylene group, B ² Represents an oxygen atom or -COO- * (provided that a bonding hand having "*" is bonded to B ³ ), B ¹ is an oxygen atom or -COO- * (provided that a bonding hand having "*" CH ₂ ) a ² ), a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.

Among the second diamine compounds of the present invention, a composition using a diamine compound having a structure represented by the formula [2b-2] of the substituent Y in the formula [2b] can increase the hydrophobicity of the resin film. Further, when the liquid crystal alignment film is used, the pretilt angle of the liquid crystal can be increased. Among these diamine compounds, a diamine compound represented by the formula [2b-28] to [2b-39] or the formula [2b-42] to the formula [2b-46] is used for the purpose of enhancing these effects . More preferred are the diamine compounds represented by the formulas [2b-24] to [2b-39] or the formulas [2b-42] to [2b-46]. In order to further improve these effects, it is preferable that these diamine compounds are contained in an amount of not less than 5 mol% and not more than 80 mol% of the total diamine component. More preferably, these diamine compounds are contained in an amount of not less than 5 mol% and not more than 60 mol% of the total diamine component from the viewpoints of coating properties of the composition and liquid crystal alignment treatment agent and electrical characteristics as a liquid crystal alignment film. And particularly preferably from 10 mol% to 60 mol% of the total diamine component.

The second diamine compound of the present invention may be one or two kinds of compounds depending on the solubility and coating properties of the specific polymer of the present invention, the orientation of the liquid crystal when the liquid crystal alignment film is formed, the voltage holding ratio, Or more can be mixed and used.

Specific polymers of the present invention may contain a diamine compound having a carboxyl group in the molecule represented by the formula [2a], a formula [2a-1] to a formula [2a-4] ], Other diamine compounds (also referred to as other diamine compounds) can be used as the diamine component.

Specific examples of the other diamine compounds are shown below, but the present invention is not limited to these examples.

Examples of other diamine compounds include 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro- , 4'-biphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2 Diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, Diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'- Aminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiamine, 3,3'-sulfonyldiamine, bis Bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl- (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, Diaminodiphenylamine, 2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl , 3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2 , 2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene , 2,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2- Bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) (3-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane, 1,4-bis Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3- Phenylene bis (methylene)] dianiline, 3, 4 '- [1,3-phenylenebis (methylene)] dianiline, 3,4' - [ 4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 '- [1,4-phenylenebis (methylene)] dianiline, 3,3' - [ Phenylene] methanone], 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [ Bis (4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (3-amino benzoate Aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) Bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N ' (1,3-phenylene) bis (4-aminobenzamide), N, N ' Aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) terephthalamide, N, N'- (Aminophenyl) isophthalamide, N, N'-bis (3-aminophenyl) isophthalamide, 9,10- Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 '-bis [ - bis (4-aminophenyl) hexafluoro Propane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, Propane, 1, 2-bis (3-aminophenoxy) propane, Bis (4-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) propane, 1,4-bis Bis (3-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,6- Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) , 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) Phenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) undecane, 1,12- Dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexyl) methane, bis 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9- , 10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

Also, as other diamine compounds, those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, and those having a large ring-shaped substituent composed of these may also be cited. Specifically, the diamine compounds represented by the following formulas [DA1] to [DA13] can be exemplified.

[Chemical Formula 45]

(46)

(47)

(Wherein [DA1] ~ formula [DA6] of, A ¹ is -COO-, -OCO-, -CONH-, -NHCO-, -CH 2 - represents, -O-, -CO- or -NH-, A ² represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(48)

(In the formula [DA7], p represents an integer of 1 to 10).

As other diamine compounds, diamine compounds represented by the following formulas [DA8] to [DA13] may be used as long as the effects of the present invention are not impaired.

(49)

(50)

[DA10], m represents an integer of 0 to 3, and n in the formula [DA13] represents an integer of 1 to 5).

In addition, as long as the effect of the present invention is not impaired, a diamine compound represented by the following formula [DA14] may be used.

(51)

(Wherein [DA14] of, A ¹ is _{-O-, -NH-, -N (CH 3} ) -, -CONH-, -NHCO-, -CH 2 O-, -OCO-, -CON (CH 3) - or -N (CH ₃ ) CO-, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, A ³ is a divalent organic group selected from -NH-, -N (CH ₃ ) -, -CONH-, -NHCO-, -COO-, -OCO-, -CON (CH ₃ ) -, -N (CH ₃ ) Or -O (CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is a nitrogen-containing aromatic heterocyclic ring, and n is an integer of 1 to 4.

In addition, as other diamine compounds, diamine compounds represented by the following formulas [DA15] and [DA16] may be used.

(52)

The above other diamine compound may be used alone or in combination of two or more types depending on the solubility of the specific polymer of the present invention in the solvent, the coating property of the composition, the orientation of the liquid crystal when the liquid crystal alignment film is formed, the voltage holding ratio, Or more may be mixed and used.

&Lt; Tetracarboxylic acid dianhydride component >

The tetracarboxylic acid component for producing the specific polymer of the present invention is preferably a tetracarboxylic acid dianhydride represented by the following formula [3] or a tetracarboxylic acid derivative thereof (also referred to as a specific tetracarboxylic acid dianhydride component) .

(53)

In the formula [3], Z ¹ is a group of at least one structure selected from the following formulas [3a] to [3j].

(54)

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ each represent a hydrogen atom or a methyl group, and may be the same or different.

Among the structures represented by the formula [3] which is the specific tetracarboxylic acid dianhydride component of the present invention, Z ¹ is preferably a tetracarboxylic acid dianhydride component represented by the formula [3a], the formula The structure represented by the formula [3c], the formula [3d], the formula [3e], the formula [3f] or the formula [3g] is preferable. More preferred is a structure represented by Formula [3a], Formula [3e], Formula [3f] or Formula [3g], and particularly preferred is Formula [3e], Formula [3f] or Formula [3g].

The specific tetracarboxylic acid dianhydride component of the present invention is preferably at least 1 mol% of the total tetracarboxylic acid component. More preferably, it is 5 mol% or more, particularly preferably 10 mol% or more.

When the specific tetracarboxylic acid dianhydride component having the structure of the formula [3e], the formula [3f] or the formula [3g] is used, the amount of the tetracarboxylic acid dianhydride component to be used is preferably 20 mol% or more of the total amount of the tetracarboxylic acid dianhydride component A desired effect can be obtained. It is preferably at least 30 mol%. Further, all of the tetracarboxylic acid dianhydride components may be a tetracarboxylic acid dianhydride component having the structure of the formula [3e], the formula [3f] or the formula [3g].

In the specific polymer of the present invention, other tetracarboxylic acid dianhydride components other than the specific tetracarboxylic acid dianhydride component may be used as long as the effect of the present invention is not impaired.

As other tetracarboxylic acid dianhydride components, tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds or dialkyl ester dihalide compounds shown below may be used as the tetracarboxylic acid dianhydride compound .

Namely, at least one of pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6 '-anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3 ' (3,4-dicarboxyphenyl) ether, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, Bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis Dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridine tetracarboxylic acid , 2,6-bis (3,4-dicarboxyphenyl) pyridine, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid or 1,3-diphenyl-1,2,3,4-cyclobutane tetracarboxylic acid The can.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component can be used in combination with the solvent for the specific polymer of the present invention, the applicability of the composition, the orientation of the liquid crystal in the case of the liquid crystal alignment film, the voltage retention rate, One kind or two or more kinds may be mixed and used depending on the characteristics of the resin.

&Lt; Process for producing specific polymer &

In the present invention, a method of synthesizing a specific polymer is not particularly limited. It is usually obtained by reacting a diamine component and a tetracarboxylic acid dianhydride component. Generally, a tetracarboxylic acid dianhydride component selected from the group consisting of a tetracarboxylic acid dianhydride and a derivative thereof is reacted with a diamine component composed of one or more diamine compounds to obtain a polyamide Get a mountain. Specifically, there are a method of polycondensing a tetracarboxylic acid dianhydride and a primary or secondary diamine compound to obtain a polyamic acid, a method of dehydrating polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound, A method of obtaining an acid or a method of polycondensing a dicarboxylic acid dihalide and a primary or secondary diamine compound to obtain a polyamic acid is used.

To obtain the polyamide acid alkyl ester, polycondensation of a tetracarboxylic acid in which a carboxylic acid group is dialkyl esterified with a primary or secondary diamine compound, a method in which a carboxylic acid group is dialkyl esterified and a dicarboxylic acid dihalide And a primary or secondary diamine compound, or a method of converting a carboxyl group of a polyamic acid into an ester is used.

To obtain the polyimide, a method of converting the above polyamic acid or polyamide acid alkyl ester into a polyimide by ring closure is used.

The reaction between the diamine component and the tetracarboxylic acid dianhydride component is usually carried out in an organic solvent with a diamine component and a tetracarboxylic acid dianhydride component. The organic solvent to be used at this time is not particularly limited as long as it dissolves the specific solvent as the component (A) of the present invention or the produced polyimide precursor.

Examples of the solvent other than the specific solvent of the present invention include the following solvents.

That is, it is preferable to use a solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

These may be used alone or in combination. In addition, even if the solvent does not dissolve the polyimide precursor, the solvent may be mixed with the polyimide precursor to the extent that the resulting polyimide precursor does not precipitate. In addition, the moisture in the organic solvent inhibits the polymerization reaction and, furthermore, causes the hydrolysis of the resulting polyimide precursor, and therefore, the organic solvent is preferably dehydrated and dried.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride component is dispersed or dissolved in the organic solvent A method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a method of alternately adding a tetracarboxylic acid dianhydride component and a diamine component, and the like, Any of these methods may be used. When a plurality of diamine components or tetracarboxylic acid dianhydride components are used to carry out the reaction, they may be reacted in a preliminarily mixed state, or they may be sequentially reacted individually, or the low molecular weight compounds reacted individually are mixed and reacted It may be a polymer. The polymerization temperature at that time may be any temperature between -20 DEG C and 150 DEG C, preferably between -5 DEG C and 100 DEG C. The reaction can be carried out at an arbitrary concentration. However, if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult. Therefore, the content is preferably 1 to 50% by mass, and more preferably 5 to 30% by mass. The reaction is carried out at a high concentration in the initial stage, and then an organic solvent can be added.

In the polymerization reaction of the polyimide precursor, the ratio of the total number of moles of the diamine component to the total number of the moles of the tetracarboxylic acid dianhydride component is preferably 0.8 to 1.2. As with the conventional polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor. In this polyimide, the closed rate (also referred to as imidization rate) of the amidic acid group does not necessarily have to be 100% Can be adjusted arbitrarily.

Examples of the method for imidizing the polyimide precursor include thermal imidization for directly heating the solution of the polyimide precursor or catalyst imidization for adding a catalyst to a solution of the polyimide precursor.

The temperature at which the polyimide precursor is thermally imidized in a solution is 100 ° C to 400 ° C, preferably 120 ° C to 250 ° C, and it is preferable that the polyimide precursor is removed while removing water generated by imidization reaction .

The catalyst imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the amide group, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to 30 moles, of the amide group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Of these, pyridine is preferred because it has a basicity suitable for proceeding the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated. The imidization rate by the catalyst imidization can be controlled by adjusting the catalyst amount, the reaction temperature, and the reaction time.

When recovering the resulting polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, the reaction solution may be introduced into a solvent and precipitated. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene and water. The polymer precipitated by charging into the solvent can be recovered by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. In addition, when the polymer precipitated and recovered is redissolved in an organic solvent, and the operation of re-precipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. As the solvent at this time, for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and when three or more kinds of solvents selected from these solvents are used, it is preferable to further increase the purification efficiency.

The molecular weight of the specific polymer of the present invention is preferably 5,000 to 1,000,000 in terms of the weight average molecular weight measured by GPC (Gel Permeation Chromatography) when the strength of the resin film or liquid crystal alignment film obtained therefrom, the workability at the time of film formation, , And more preferably 10,000 to 150,000.

The specific polysiloxane as the component (C) of the present invention is a polysiloxane obtained by polycondensation of an alkoxysilane containing any one of the alkoxysilanes represented by the above-mentioned formula [A1], formula [A2] or formula [A3].

The alkoxysilane represented by the formula [A1] of the present invention is an alkoxysilane represented by the following formula [A1].

(55)

In the formula [A1], A ¹ is an organic group having 8 to 35 carbon atoms and having an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, a heterocyclic ring or a steroid structure.

In the formula [A1], A ² are each a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [A1], A ³ is an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable in terms of the polycondensation reactivity.

In the formula [A1], m is an integer of 1 or 2. Among them, 1 is preferable in terms of synthesis.

In the formula [A1], n is an integer of 0 to 2.

In the formula [A1], p is an integer of 0 to 3. Among them, an integer of 1 to 3 is preferable in terms of polycondensation reactivity. More preferably 2 or 3.

In the formula [A1], m + n + p is 4.

Specific examples of the alkoxysilane represented by the formula [A1] include octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, Heptadecyltrimethoxysilane, hexadecyltriethoxysilane, pentyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane , Nonadecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, m-styrylethyltrimethoxysilane, p-styrylethyltrimethoxysilane, 1-naphthyltrimethoxysilane, 1-naphtyltrimethoxysilane, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, Ethoxy phenyl silane, and the like.

In addition, alkoxysilanes represented by the following formulas [A1-1] to [A1-32] may be used.

(56)

(57)

(58)

[Chemical Formula 59]

(60)

(61)

(62)

(63)

&Lt; EMI ID =

(Wherein [A1-1] ~ formula [A1-18], R ¹ represents an alkyl group having 1 to 5 carbon atoms each).

(65)

(In the formulas [A1-19] to formula [A1-22], R ¹ represents an alkyl group having 1 to 5 carbon atoms, and R ² each represent -O-, -COO-, -OCO-, -CONH-, _{NHCO-, -CON (CH 3) -} , -N (CH 3) CO-, -OCH 2 -, -CH 2 O-, -COOCH 2 - or denotes a -CH ₂ OCO-, R ³ are each C 1 An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(66)

(Wherein [A1-23] and formula [A1-24] of, R ¹ each represent an alkyl group of a carbon number of 1 ~ 5, R ² are each -O-, -COO-, -OCO-, -CONH-, - _{NHCO-, -CON (CH 3) -} , -N (CH 3) CO-, -OCH 2 -, -CH 2 O-, -COOCH 2 - or denotes a -CH ₂ OCO-, R ³ are each C 1 An alkoxy group, a fluorine-containing alkyl group, a fluorine-containing alkoxy group, a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.

(67)

(68)

(Wherein [A1-25] ~ formula [A1-31] of, R ¹ each represent an alkyl group of a carbon number of 1 ~ 5, R ² are each -O-, -COO-, -OCO-, -CONH-, - _{NHCO-, -CON (CH 3) -} , -N (CH 3) CO-, -OCH 2 -, -CH 2 O-, -COOCH 2 - or denotes a -CH ₂ OCO-, R ³ are each C 1 An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(69)

(In the formula [A1-32], R ¹ represents an alkyl group of 1 to 5 carbon atoms, B ⁴ represents an alkyl group of 3 to 20 carbon atoms which may be substituted with a fluorine atom, B ³ represents 1,4-cyclohexylene And B ² represents an oxygen atom or COO- * (provided that a bonding hand having "*" is bonded to B ³ ), B ¹ represents an oxygen atom or COO- * (However, the combined hand with "*" is combined with (CH ₂ ) a ² ). A ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1).

The alkoxysilane represented by the above formula [A1] can be suitably selected depending on the strength of the resin film or the liquid crystal alignment film, the workability at the time of film formation, furthermore, the properties such as liquid crystal alignment property, voltage holding ratio, One kind or two or more kinds may be mixed and used.

The alkoxysilane represented by the formula [A2] of the present invention is an alkoxysilane represented by the following formula [A2].

(70)

In formula [A2], B ¹ is an organic group having 2 to 12 carbon atoms and having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacrylic group, an acrylic group, a ureide group or a cinnamoyl group. Among them, a vinyl group, an epoxy group, an amino group, a methacrylic group, an acrylic group or an ureide group is preferable in view of easiness of obtaining. More preferably a methacryl group, an acrylic group or a ureide group.

In the formula [A2], B ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [A2], B ³ is an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable in terms of the polycondensation reactivity.

In the formula [A2], m is an integer of 1 or 2. Among them, 1 is preferable in terms of synthesis.

In the formula [A2], n is an integer of 0 to 2.

In the formula [A2], p is an integer of 0 to 3. Among them, an integer of 1 to 3 is preferable in terms of polycondensation reactivity. More preferably 2 or 3.

In the formula [A2], m + n + p is 4.

Specific examples of the alkoxysilane represented by the formula [A2] include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, Vinyltris (2-methoxyethoxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxy Silane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, diethoxy (3-glycidyloxypropyl) methylsilane, 3-glycidyloxypropyl (dimethoxy) (3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- Aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-amino (Trimethoxy) methylsilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (Triethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl methacrylate, (Triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 3- (triethoxysilyl) ethyl methacrylate, 3- (Triethoxysilyl) ethyl acrylate, 3- (trimethoxysilyl) ethyl acrylate, 3- (triethoxysilyl) methyl methacrylate, 3- (Triethoxysilyl) methyl acrylate, 3- (trimethoxysilyl) methyl acrylate, γ-ureide propyl (R) -N (R) -N-1-phenylethyl-N'-triethoxysilylpropylurea,? -Ureidopropyltrimethoxysilane,? -Ureidopropyltripropoxysilane, Propyl] urea, bis [3- (trimethoxysilyl) propyl] urea, bis [3- (tripropoxysilyl) propyl] urea, 1- [3- Trimethoxysilyl) propyl] urea and the like.

The alkoxysilane represented by the above-mentioned formula [A2] can be suitably selected depending on the strength of the resin film or the liquid crystal alignment film, the workability at the time of film formation, furthermore, the properties such as liquid crystal alignment property, voltage retention rate, One kind or two or more kinds may be mixed and used.

The alkoxysilane represented by the formula [A3] of the present invention is an alkoxysilane represented by the following formula [A].

(71)

In the formula [A3], D ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be substituted with a halogen atom, a nitrogen atom, an oxygen atom or a sulfur atom. Among them, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.

In the formula [A3], D ² is an alkyl group having 1 to 5 carbon atoms. Among them, an alkyl group having 1 to 3 carbon atoms is preferable in terms of the polycondensation reactivity.

In the formula [A3], n is an integer of 0 to 3.

Specific examples of the alkoxysilane represented by the formula [A3] include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxy Examples of the silane coupling agent include silane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethoxydiethylsilane, dibutoxydimethylsilane, ) Triethoxysilane, 3-chloropropyldimethoxymethylsilane, 3-chloropropyltriethoxysilane, 2-cyanoethyltriethoxysilane, trimethoxy (3,3,3-trifluoropropyl) silane , Hexyltrimethoxysilane, 3-trimethoxysilylpropyl chloride, and the like.

Examples of the alkoxysilane of the formula [A3] wherein n is 0 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane.

The alkoxysilane represented by the above-mentioned formula [A3] is preferably used in an amount of from 0.01 to 10 parts by weight, based on the strength of the resin coating film or the liquid crystal alignment film, the workability at the time of film formation, furthermore, the liquid crystal alignment property, One kind or two or more kinds may be mixed and used.

The specific polysiloxane of the present invention is a polysiloxane obtained by polycondensation of an alkoxysilane containing any one of the alkoxysilanes represented by the above-mentioned formula [A1], formula [A2] or formula [A3] Is preferably a polysiloxane obtained by polycondensation of an alkoxysilane. That is, the alkoxysilane containing two kinds of the above-mentioned formula [A1] and the formula [A2], the formula [A1] and the formula [A3] or the formula [A2] and the formula [A3] ], The formula [A2] and the formula [A3]. Among them, the alkoxysilane containing two kinds of the above-mentioned formula [A1] and the formula [A2], the formula [A1] and the formula [A3], or the alkoxysilane of the formula [A1], the formula [A2] Alkoxysilane containing three species is preferable.

The alkoxysilane represented by the formula [A1], the formula [A2] or the formula [A3] is used for obtaining the specific polysiloxane of the present invention.

The alkoxysilane represented by the formula [A1] is preferably 1 to 40 mol%, more preferably 1 to 30 mol%, of all the alkoxysilanes.

The alkoxysilane represented by the formula [A2] is preferably 1 to 70 mol%, more preferably 1 to 60 mol%, of all the alkoxysilanes.

The alkoxysilane represented by the formula [A3] is preferably 1 to 99 mol%, more preferably 1 to 80 mol%, of all the alkoxysilanes.

The method for obtaining the specific polysiloxane used in the present invention is not particularly limited. The specific polysiloxane of the present invention is obtained by polymerizing an alkoxysilane containing any one of the alkoxysilanes represented by the above-mentioned formula [A1], formula [A2] or formula [A3] in an organic solvent, Can be obtained by polymerizing a plurality of alkoxysilanes among the alkoxysilanes represented by the formulas [A1], [A2] and [A3] in an organic solvent. The specific polysiloxane of the present invention is obtained as a solution in which an alkoxysilane is polycondensed and uniformly dissolved in an organic solvent.

The method of polycondensation of the specific polysiloxane of the present invention is not particularly limited. Among them, for example, a method of subjecting an alkoxysilane to a hydrolysis and polycondensation reaction in a specific solvent, an alcohol solvent or a glycol solvent of the present invention. At this time, in order to adjust the composition of the present invention or the liquid crystal alignment treatment agent, it is preferable to use the specific solvent of the present invention.

The hydrolysis-polycondensation reaction may be partially hydrolyzed or completely hydrolyzed. In the case of complete hydrolysis, theoretically, 0.5-fold molar amount of water of all alkoxy groups in the alkoxysilane may be added, and it is usually preferable to add an excess amount of water in excess of 0.5-fold molar amount. In order to obtain the specific polysiloxane of the present invention, the amount of water used in the hydrolysis and polycondensation reaction may be appropriately selected according to the purpose, but is preferably 0.5 to 2.5 times the molar amount of all the alkoxy groups in the alkoxysilane.

For the purpose of accelerating the hydrolysis and polycondensation reaction, an acidic compound such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid, maleic acid or fumaric acid, ammonia, methylamine, ethylamine, ethanolamine or triethylamine Or a catalyst such as a metal salt such as hydrochloric acid, nitric acid or nitric acid can be used. In addition, the hydrolysis-polycondensation reaction may be promoted by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected depending on the purpose. For example, heating and stirring at 50 DEG C for 24 hours, and then heating and stirring for 1 hour under reflux.

As another method of polycondensation, there is a method of heating a mixture of alkoxysilane, organic solvent and oxalic acid to perform polycondensation reaction. Specifically, oxalic acid is added to a specific solvent or alcohol solvent of the present invention in advance to prepare a solution of oxalic acid, and then the solution is heated to mix the alkoxysilane. At this time, the amount of oxalic acid to be used in the above reaction is preferably 0.2 to 2.0 mol per 1 mol of all alkoxy groups in the alkoxysilane. This reaction can be carried out at a temperature of the solution of 50 to 180 ° C, but is preferably carried out for several tens of minutes to several tens of hours under reflux so as not to evaporate or volatilize the solvent.

In the case of using a plurality of alkoxysilanes represented by the above formulas [A1], [A2] and [A3] in the polycondensation reaction for obtaining the specific polysiloxane of the present invention, Or may be reacted while sequentially adding a plurality of kinds of alkoxysilanes.

The solvent used in the polycondensation reaction of the alkoxysilane is not particularly limited as long as it dissolves the alkoxysilane. In addition, even a solvent in which alkoxysilane is not dissolved may be used as long as it dissolves with progress of the polycondensation reaction of alkoxysilane. As a solvent used in the condensation reaction, an alcohol is generally generated by a polycondensation reaction of an alkoxysilane, and thus an organic solvent having good compatibility with an alcohol solvent, a glycol solvent, a glycol ether solvent or an alcohol is used . Specific examples of the solvent to be used in the polycondensation reaction include alcohol solvents such as methanol, ethanol, propanol, butanol or diacetone alcohol, alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, Butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol Glycol solvents such as diol, 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol or 1,6-hexanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, Propyl ether, Ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether , Glycol ether solvents such as propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether or propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, And an alcohol such as 2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphotriapamide or m- And an organic solvent having good phase compatibility.

Among them, it is preferable to use the specific solvent of the present invention in adjusting the composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention. In the present invention, at the time of the polycondensation reaction, one or two or more kinds of the above-mentioned solvents may be mixed and used.

Solution polymerization of a specific polysiloxane obtained by the above method, it is preferred that one (also referred to as SiO ₂ in terms of concentration) of the total alkoxy silane silicon atom to a concentration in terms of SiO ₂ having not more than 20% by weight added as a raw material. In particular, it is preferably 5 to 15% by mass. By selecting an arbitrary concentration in this concentration range, the generation of gel in the solution can be suppressed, and a uniform polycondensation solution of the specific polysiloxane can be obtained.

In the present invention, the polycondensation solution of the specific polysiloxane obtained by the above method may be directly used as the solution of the specific polysiloxane of the component (C) of the present invention. If necessary, the polycondensation solution of the specific polysiloxane obtained by the above- , Or a solution of the specific polysiloxane of component (C) may be prepared by diluting with a solvent or by substituting with another solvent.

The solvent (also referred to as an addition solvent) to be used in the dilution by adding the solvent may be a solvent used for the polycondensation reaction, a specific solvent of the present invention, or other solvent. This addition solvent is not particularly limited as far as the specific polysiloxane is uniformly dissolved, and one or more kinds of the addition solvent can be arbitrarily selected and used. As such an additive solvent, in addition to the solvent used for the polycondensation reaction, a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone, an ester solvent such as methyl acetate, ethyl acetate or ethyl lactate, .

In the present invention, it is preferable that the specific polysiloxane of the component (C) be distilled off at a normal pressure or a reduced pressure, the alcohol generated during the polycondensation reaction of the specific polysiloxane before mixing with the specific polymer of the component (B).

The composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention is a coating solution for forming a resin coating or a liquid crystal alignment layer (collectively referred to as a resin coating), and is a coating solution for forming a resin coating containing a specific solvent, a specific polymer and a specific polysiloxane Coating solution. Among them, the polymer of the present invention in the composition or the liquid crystal alignment treatment agent using the composition is a specific polymer and a specific polysiloxane.

The content of the specific polysiloxane in the composition of the present invention or the liquid crystal alignment treatment agent using the composition is preferably 0.1 to 90 parts by mass with respect to 100 parts by mass of the specific polymer component. Among them, from the viewpoint of the stability of the composition or the liquid crystal alignment treatment agent, 1 to 70 parts by mass is more preferable relative to 100 parts by mass of the specific polymer. Particularly preferably 5 to 60 parts by mass.

In the composition of the present invention or the liquid crystal alignment treatment agent using the composition, all the polymer components may be the polymer of the present invention, and the polymer of the present invention may be mixed with other polymers. At that time, the content of the other polymer is 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass, of the polymer of the present invention. Examples of the other polymer include a polyimide precursor or polyimide that does not use a diamine compound having a carboxyl group, a second diamine compound, or a specific tetracarboxylic acid component. Further, polymers other than polyimide precursors and polyimides, specifically, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, and the like can be given.

The organic solvent in the composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention preferably has an organic solvent content of 70 to 99.9 mass% from the viewpoint of forming a uniform resin film by coating. This content can be appropriately changed depending on the film thickness of the intended resin film or liquid crystal alignment film.

In the organic solvent used in the composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention, all the organic solvents may be the specific solvents of the present invention, and the organic solvents of the present invention may be mixed with other organic solvents . At this time, the specific solvent of the present invention is preferably 50 to 100% by mass of the entire solvent contained in the composition or the liquid crystal alignment treatment agent. Among these, 55 to 100 mass% is preferable. More preferred is 55 to 95 mass%.

The other organic solvent is not particularly limited as long as it is an organic solvent that dissolves a specific polymer and a specific polysiloxane. Specific examples thereof are given below.

Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N- 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone.

Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or? -Butyllactone (also referred to as component (D)).

These components (D) are preferably contained in an amount of 1 to 50% by mass of the entire organic solvent contained in the composition or the liquid crystal alignment treatment agent using the composition. Among them, 1 to 40% by mass is preferable. More preferably, it is 1 to 30% by mass, and more preferably 5 to 30% by mass.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention can be used in an organic solvent for improving the coating film property or surface smoothness of the resin film or liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent using the composition is applied, , That is, a poor solvent can be used.

Specific examples of the poor solvent for improving the coating film property and surface smoothness of the resin coating film or liquid crystal alignment film are shown below.

Butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, Butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl- Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-propanediol, Butanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4- (2-ethylhexyl) acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, 2- (methoxymethoxy) ethanol, ethylene glycol monoisoprene Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, 2- (hexyloxy) ethanol, Alcohols, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopro Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, Ethylene glycol monoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2- Diethyleneglycol monomethyl ether, triethylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, isopropyl acetate, Acetic acid Propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3- Is a solvent having a low surface tension of a solvent such as propyl propionate, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or lactic acid isoamyl ester.

Among them, 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, It is preferable to use ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether or propylene glycol monobutyl ether (also referred to as component (E)).

These components (E) are preferably contained in an amount of 1 to 50 mass% of the entire organic solvent contained in the composition or the liquid crystal alignment treatment agent using the composition. In particular, it is preferably 1 to 45% by mass. More preferably, it is 5 to 45% by mass, and more preferably 5 to 40% by mass.

As long as the effect of the present invention is not impaired, the composition of the present invention or the liquid crystal alignment treatment agent using the composition may contain a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group , Or a crosslinkable compound having at least one kind of substituent selected from the group consisting of a polymerizable unsaturated bond may be introduced. These substituent groups and polymerizable unsaturated bonds need to have two or more in the crosslinkable compound.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolak epoxy resin, triglycidyl isocyanurate, tetraglycidyl amino diphenylene , Tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetate Diglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis 2- (4- (2,3-epoxypropoxy) phenyl) -2- (4-methylpentanoyloxyphenyl) octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl methadienyldiamine, 2- (4- (1, 4- (2,3-epoxypropoxy) phenyl) ethyl) phenyl) propane or 1,3- Oxy) phenyl) -1- (4- (1- (4- (2,3-epoxypropoxy) phenyl) -1-methylethyl) phenyl) ethyl) phenoxy) -2-propanol.

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].

(72)

Specifically, it is a crosslinkable compound represented by the following formulas [4-1] to [4-11].

(73)

(In the formula [4-1], n represents an integer of 1 to 3).

&Lt; EMI ID =

(75)

[Formula 76]

(4-7), n represents an integer of 1 to 3, and n in the formula [4-8] represents an integer of 1 to 3, and n in the formula [4-9] Lt; / RTI >

[Formula 77]

(In the formula [4-11], n represents an integer of 1 to 10).

The crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].

(78)

Specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-37].

(79)

(80)

[Formula 81]

(82)

(83)

(84)

(85)

&Lt; EMI ID =

[Chemical Formula 87]

[Formula 88]

(89)

(90)

(In the formula [5-24], n represents an integer of 1 to 10, and in the formula [5-25], n represents an integer of 1 to 10).

[Formula 91]

&Lt; EMI ID =

&Lt; EMI ID =

(94)

&Lt; EMI ID =

(In the formula [5-36], n represents an integer of 1 to 100, and in the formula [5-37], n represents an integer of 1 to 10).

Also, a polysiloxane having at least one structure represented by the following formulas [5-38] to [5-40] may be used.

&Lt; EMI ID =

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, a carbon number An alkyl group, an alkoxyl group, an aliphatic ring or an aromatic ring, and at least one of them represents a structure represented by the formula [5].

More specifically, the compounds of the following formulas [5-41] and [5-42] can be mentioned.

[Formula 97]

(In the formula [5-42], n represents an integer of 1 to 10).

Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group such as a melamine resin, Guanamine resin, glycoluril-formaldehyde resin, succinylamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a melamine derivative in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group, a benzoguanamine derivative, or glycoluril can be used. The melamine derivative or the benzoguanamine derivative may be present as a dimer or trimer. They preferably have 3 to 6 on average of a methylene group or an alkoxymethyl group per one triazine ring.

Examples of such a melamine derivative or benzoguanamine derivative include MX-750 in which a methoxymethyl group is substituted in an average of 3.7 methoxymethyl groups per one triazine ring of a commercial product, MW having an average of 5.8 methoxymethyl groups per triazine ring -30 (manufactured by Sanwa Chemical Co., Ltd.) or methoxymethylated melamine such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236, 238, 212, 253 , 254 and the like, butoxymethylated melamines such as Cymel 506 and 508, carboxyl-containing methoxymethylated isobutoxymethylated melamines such as Cymel 1141, and methoxymethylated ethoxymethylated melamines such as Cymel 1123 Methoxymethylated butoxymethylated benzoguanamine such as benzoguanamine, Cymel 1123-10, butoxymethylated benzoguanamine such as Cymel 1128, carboxyl-containing methoxymethylated methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80, And anamine (manufactured by Mitsui Cyanamid Co., Ltd.). Examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylated glycoluril such as Powderlink 1174, and the like.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1 , 4-bis (sec-butoxymethyl) benzene, or 2,6-dihydroxymethyl-p-tert-butylphenol.

More specifically, there are listed crosslinkable compounds represented by the formulas [6-1] to [6-48], which are listed on pages 62 to 66 of International Publication WO2011 / 132751 have.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri ) Acryloyloxyethoxytrimethylol propane or glycerin polyglycidyl ether poly (meth) acrylate, and also crosslinkable compounds having three polymerizable unsaturated groups in the molecule, such as ethylene glycol di (meth) acrylate, di Acrylates such as ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di Di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol di (Meth) acrylate such as di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate or hydroxypivalic acid neopentyl glycol di (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy 2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxypropyl , 2- ( Bit), and the cross-linking compound having one polymerizable unsaturated group in the molecule, such as acryloyloxyethyl phosphate ester, or N- methyl-roll (meth) acrylamide.

In addition, a compound represented by the following formula [7] may be used.

(98)

(Wherein E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring) And E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

[Formula 99]

The above compound is an example of a crosslinkable compound, but is not limited thereto. The crosslinkable compound used in the composition of the present invention or the liquid crystal alignment treatment agent using the composition may be of one kind, or may be a combination of two or more kinds.

The content of the crosslinkable compound in the composition of the present invention or the liquid crystal alignment treatment agent using the composition is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. In order for the crosslinking reaction to proceed to exhibit the intended effect, the amount is more preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, per 100 parts by mass of all the polymer components.

As a compound for promoting charge transfer in the liquid crystal alignment film and promoting charge detachment of the liquid crystal cell using the liquid crystal alignment film when the liquid crystal alignment treatment agent using the composition of the present invention is used as a liquid crystal alignment film, It is preferable to add a nitrogen-containing heterocyclic amine compound represented by the formula [M1] to the formula [M156], which is disclosed in pages 69 to 73 of the publication entitled " The amine compound may be added directly to the composition, but it is preferable to add the amine compound in an appropriate solvent at a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass. This solvent is not particularly limited as long as it is an organic solvent for dissolving the above-mentioned polymer.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition can improve the uniformity of the film thickness or the surface smoothness of the resin film or the liquid crystal alignment film when the composition or the liquid crystal alignment treatment agent using the composition is applied, May be used. Further, a compound for improving the adhesion of the resin film or the liquid crystal alignment film to the substrate may be used.

Examples of the compound that improves the uniformity of the thickness of the resin film or the liquid crystal alignment film and the surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.

More specifically, for example, EF301, EF303 and EF352 (manufactured by Tohchem Products), Megafac F171, F173 and R-30 (manufactured by Dainippon Ink & Chemicals, Inc.), Fluorad FC430 and FC431 (Available from Sumitomo 3M), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent.

Specific examples of the compound improving the adhesion between the resin film or the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.

For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3 3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxy (3-aminopropyl) Aminopropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, N-trimethoxysilylpropyltriethoxysilane, Amine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl Acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 Tetraglycidyl-2,4-hexanediol, N, N, N ', N', -tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylamino Methyl) cyclohexane or N, N, N ', N', -tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

When a compound which adheres to these substrates is used, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the composition or the liquid crystal alignment treatment agent using the same. If the amount is less than 0.1 part by mass, the effect of improving the adhesion can not be expected. If the amount is more than 30 parts by mass, the storage stability of the composition or the liquid crystal alignment treatment agent using the composition may be deteriorated.

The composition of the present invention or the liquid crystal alignment treatment agent using the composition of the present invention may contain, in addition to the compound for improving the uniformity of the film thickness of the poor solvent, the crosslinkable compound, the resin film or the liquid crystal alignment film, If the effect is not impaired, a dielectric material or a conductive material may be added for the purpose of changing electrical characteristics such as the dielectric constant and conductivity of the resin film or the liquid crystal alignment film.

&Lt; Resin Coating >

The composition of the present invention can be used as a resin film after being coated and baked on a substrate. As the substrate to be used at this time, a glass substrate, a silicon wafer, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, etc. may be used depending on the intended device. The method of applying the composition is not particularly limited, but a method of industrially performing the method by dip coating, roll coating, slit coating, spinner coating, spray coating, screen printing, offset printing, It is common. They may be used according to the purpose.

After the composition is applied onto the substrate, the solvent is evaporated at 50 to 300 deg. C, preferably 80 to 250 deg. C by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) can do. The thickness of the resin film after firing can be adjusted to 0.01 to 100 탆, depending on the purpose.

The liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and subjected to an orientation treatment by rubbing treatment, light irradiation, or the like. Further, in the case of vertical alignment application, etc., it can be used as a liquid crystal alignment film without alignment treatment. The substrate to be used at this time is not particularly limited as long as it is a substrate having high transparency. In addition to the glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of process simplification, it is preferable to use a substrate on which an ITO electrode or the like for liquid crystal driving is formed. In a reflection type liquid crystal display element, an opaque substrate such as a silicon wafer can be used only for a substrate on one side, and as the electrode in this case, a material for reflecting light such as aluminum can also be used.

The method of applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, or inkjet printing is generally used. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and they may be used depending on the purpose.

After the liquid crystal alignment treatment agent is applied onto the substrate, the solvent is evaporated at a temperature of 50 to 300 ° C, preferably 80 to 250 ° C by a heating means such as a hot plate, a heat circulation type oven or an IR (infrared) An alignment film can be formed. When the thickness of the liquid crystal alignment layer after firing is excessively large, the power consumption of the liquid crystal display element is disadvantageously deteriorated. When the thickness is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, the thickness is preferably 5 to 300 nm Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired liquid crystal alignment film is treated by rubbing, polarized ultraviolet irradiation, or the like.

In the liquid crystal display element of the present invention, a substrate having a liquid crystal alignment film attached thereto from the liquid crystal alignment treatment agent of the present invention is obtained by the above-mentioned technique, and then a liquid crystal cell is produced by a known method to form a liquid crystal display element.

As a manufacturing method of the liquid crystal cell, a pair of substrates having a liquid crystal alignment film formed thereon is prepared, a spacer is scattered on the liquid crystal alignment film of the substrate of one substrate, and the substrates of the other substrate are bonded A method in which a liquid crystal is injected under reduced pressure and sealed or a method in which a liquid crystal is dropped on a surface of a liquid crystal alignment film on which a spacer is dispersed and a substrate is then subjected to sealing to perform sealing.

The liquid crystal alignment treatment agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes and includes a polymerizable compound polymerized by at least one of active energy rays and heat between a pair of substrates And then polymerizing the polymerizable compound by at least one of irradiation of an active energy ray and heating, while applying a voltage between electrodes, is preferably used for a liquid crystal display device. Here, as the active energy ray, ultraviolet rays are suitable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, irradiation with ultraviolet rays and heating may be simultaneously performed.

The liquid crystal display element controls a pretilt of a liquid crystal molecule by a PSA (Polymer Sustained Alignment) method. In the PSA method, a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer, is incorporated into a liquid crystal material, and after a liquid crystal cell is assembled, a predetermined voltage is applied to the liquid crystal layer, Ultraviolet rays or the like is irradiated, and the pre-tilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is produced is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field or the like formed on the liquid crystal layer. Further, the PSA method is suitable for forming a vertically aligned liquid crystal layer which is difficult to control pre-tilt by rubbing treatment because no rubbing treatment is required.

That is, in the liquid crystal display element of the present invention, a liquid crystal alignment treatment agent of the present invention is provided with a liquid crystal alignment film-attached substrate obtained by the above-mentioned technique, and then a liquid crystal cell is produced, The orientation of the liquid crystal molecules can be controlled by polymerizing the compound.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, a spacer is dispersed on the liquid crystal alignment film of the substrate of the single chamber, and the liquid crystal alignment film surface is made inward, A method in which a liquid crystal is injected under reduced pressure and sealed, or a method in which liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed, and then the substrate is sealed to perform a sealing.

The liquid crystal is mixed with a polymerizable compound which is polymerized by irradiation with heat or ultraviolet rays. Examples of the polymerizable compound include a compound having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule. At that time, the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the liquid crystal component. If the amount of the polymerizable compound is less than 0.01 part by mass, the alignment of the liquid crystal can not be controlled because the polymerizable compound is not polymerized. If more than 10 parts by mass, the unreacted polymerizable compound increases and the baking property of the liquid crystal display element deteriorates do.

After the liquid crystal cell is manufactured, the polymerizable compound is polymerized by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell. Thus, the orientation of the liquid crystal molecules can be controlled.

In addition, the liquid crystal alignment treatment agent of the present invention comprises a liquid crystal layer between a pair of substrates provided with electrodes, and includes a polymerizable group which is polymerized by at least one of active energy rays and heat between the pair of substrates And a liquid crystal display device manufactured by a process of applying a voltage between electrodes. Here, as the active energy ray, ultraviolet rays are suitable. The ultraviolet ray has a wavelength of 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 占 폚, preferably 60 to 80 占 폚. In addition, irradiation with ultraviolet rays and heating may be simultaneously performed.

In order to obtain a liquid crystal alignment film containing a polymerizable group polymerizing from at least one of active energy ray and heat, a method of adding a compound containing this polymerizable group to a liquid crystal alignment treatment agent, a method of using a polymer component containing a polymerizable group . Since the liquid crystal alignment treatment agent of the present invention contains a specific compound having a double bonding site that reacts by irradiation with heat or ultraviolet rays, the orientation of the liquid crystal molecules can be controlled by at least one of irradiation with ultraviolet rays and heating have.

For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of the substrate of one substrate, and the substrates of the other substrate are laminated so that the liquid crystal alignment film surface is inward A method in which a liquid crystal is injected under reduced pressure and a method in which a liquid crystal is dropped on the surface of a liquid crystal alignment film on which a spacer is dispersed and a substrate is then subjected to sealing to effect sealing.

After the liquid crystal cell is manufactured, the orientation of the liquid crystal molecules can be controlled by applying heat or ultraviolet rays while applying alternating current or direct current voltage to the liquid crystal cell.

As described above, the liquid crystal display device manufactured using the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a liquid crystal television of a large screen and high precision.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Abbreviations used in Synthesis Examples, Examples and Comparative Examples are as follows.

(Diamine compound having a carboxyl group)

A1: 3,5-diaminobenzoic acid (diamine compound represented by the following formula [A1]):

A2: 2,5-diaminobenzoic acid (diamine compound represented by the following formula [A2]):

(100)

(Second diamine compound)

B1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (diamine compound represented by the following formula [B1]

B2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (diamine compound represented by the following formula [B2]

B3: 1,3-Diamino-4- {trans 4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy} benzene (diamine compound represented by the following formula [B3]

B4: diamine compound represented by the following formula [B4]

B5: 1,3-Diamino-4-octadecyloxybenzene (diamine compound represented by the following formula [B5]):

B6: diamine compound represented by the following formula [B6]

(101)

&Lt; EMI ID =

&Lt; EMI ID =

(Other diamine compound)

C1: p-phenylenediamine (diamine compound represented by the following formula [C1]):

C2: m-phenylenediamine (diamine compound represented by the following formula [C2]):

&Lt; EMI ID =

(Tetracarboxylic acid component)

D1: 1,2,3,4-Cyclobutanetetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride represented by the following formula [D1]):

D2: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid dianhydride (tetracarboxylic acid dianhydride represented by the following formula [D2]

D3: tetracarboxylic acid dianhydride represented by the following formula [D3]

D4: tetracarboxylic acid dianhydride represented by the following formula [D4]

&Lt; EMI ID =

(Alkoxysilane monomer)

MPMS: 3-methacryloxypropyltrimethoxysilane (alkoxysilane monomer represented by the formula [A2] of the present invention)

UPS: 3-ureide propyltriethoxysilane (alkoxysilane monomer represented by the formula [A2] of the present invention)

TEOS: tetraethoxysilane (alkoxysilane monomer represented by the formula [A3] of the present invention)

(Component (A) (specific solvent) of the present invention)

DEME: diethylene glycol monomethyl ether (solvent represented by the formula [1-1] of the present invention)

DEEE: Diethylene glycol monoethyl ether (the solvent represented by the formula [1-2] of the present invention)

&Lt; EMI ID =

(Component (D) (other organic solvent) of the present invention)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

? -BL:? -butyrolactone

(Component (E) (other organic solvent) of the present invention)

BCS: ethylene glycol monobutyl ether

(Measurement of molecular weight of polyimide precursor and polyimide)

The molecular weights of the polyimide precursor and polyimide in the synthesis examples were measured using a gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko K.K.), a column (KD-803, KD-805) ) Was used, and measurement was carried out as follows.

Column temperature: 50 ° C

Eluent: N, N'- dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 m㏖ / ℓ (L), phosphoric acid anhydrous crystal (o- phosphoric acid) is 30 m㏖ / ℓ , Tetrahydrofuran (THF) of 10 ml / l)

Flow rate: 1.0 ml / min

Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: about 12,000, 4,000, and 1,000 manufactured by Polymer Laboratories) .

(Measurement of imidization ratio of polyimide)

The imidization rate of the polyimide in the synthesis example was measured as follows. (DMSO-d6, 0.05 mass% TMS (tetramethylsilane)) mixture was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, phi 5 Product) (0.53 ml) was added, and completely dissolved by applying ultrasonic waves. This solution was subjected to proton NMR measurement at 500 MHz using an NMR measuring instrument (JNW-ECA500) (manufactured by Nippon Dental Electronics Co., Ltd.). A proton originating from a structure which does not change before and after imidation is defined as a reference proton and the peak integration value of the proton and the proton peak integration value derived from the NH group of the amide acid appearing in the vicinity of 9.5 ppm to 10.0 ppm By using the following formula.

Imidization ratio (%) = (1 -? X / y) x 100

In the above formula, x is the proton peak integrated value derived from the NH group of the amide acid, y is the peak integrated value of the reference proton, and? Is the NH of the amide acid when the polyamic acid (imidization ratio is 0% The ratio of the number of reference protons to one protopertone.

&Quot; Synthesis of specific polymer (polyimide precursor and polyimide) which is component (B) of the present invention "

&Lt; Synthesis Example 1 &

A mixture of D1 (3.55 g, 18.1 mmol) and A1 (2.75 g, 18.1 mmol) in DEEE (56.7 g) was reacted at 40 ° C for 8 hours to obtain a polyamic acid solution ). The polyamic acid had a number average molecular weight of 12,100 and a weight average molecular weight of 27,100.

&Lt; Synthesis Example 2 &

D2 (9.34 g, 37.3 mmol) and A2 (7.10 g, 46.7 mmol) were mixed in NMP (30.1 g) and reacted at 80 ° C for 5 hours. Then, D1 (1.83 g, 9.33 mmol) and NMP 24.7 g) was added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (6.52 g) and pyridine (5.05 g) were added as an imidization catalyst and reacted at 90 ° C for 4 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (2). The imidization ratio of the polyimide was 54%, the number average molecular weight was 13,400, and the weight average molecular weight was 34,500.

&Lt; Synthesis Example 3 &

D2 (2.11 g, 8.43 mmol), B1 (2.67 g, 7.02 mmol) and A1 (1.07 g, 7.03 mmol) were mixed in DEEE (34.4 g) and reacted at 80 ° C for 5 hours. 1.10 g, 5.61 mmol) and DEEE (28.1 g) were added and reacted at 40 占 폚 for 8 hours to obtain a polyamic acid solution (3) having a resin solid content concentration of 10.0% by mass. This polyamic acid had a number average molecular weight of 12,900 and a weight average molecular weight of 35,500.

&Lt; Synthesis Example 4 &

D2 (4.06 g, 16.2 mmol), B1 (5.14 g, 13.5 mmol) and A1 (2.06 g, 13.5 mmol) were mixed in NMP (22.1 g) 2.12 g, 10.8 mmol) and NMP (18.1 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.16 g) and pyridine (4.00 g) were added as an imidation catalyst and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (4). The imidization ratio of the polyimide was 60%, the number average molecular weight was 14,300, and the weight average molecular weight was 37,100.

&Lt; Synthesis Example 5 &

A mixture of D2 (6.02 g, 24.1 mmol), B1 (4.58 g, 12.0 mmol), A1 (2.29 g, 15.1 mmol) and C1 (0.33 g, 3.05 mmol) in NMP (23.8 g) (1.18 g, 6.02 mmol) and NMP (19.4 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.33 g) and pyridine (4.13 g) were added as imidation catalysts and reacted at 80 ° C for 2 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (5). The imidization ratio of the polyimide was 58%, the number average molecular weight was 15,100, and the weight average molecular weight was 37,800.

&Lt; Synthesis Example 6 &

(2.3 g, 9.28 mmol), A1 (2.35 g, 15.4 mmol) and B6 (1.26 g, 6.20 mmol) were mixed in NMP (23.9 g) (1.82 g, 9.28 mmol) and NMP (19.6 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.50 g) and pyridine (4.25 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (6). The imidization ratio of the polyimide was 50%, the number average molecular weight was 18,500, and the weight average molecular weight was 42,700.

&Lt; Synthesis Example 7 &

A mixture of D2 (5.51 g, 22.0 mmol), B3 (4.08 g, 9.43 mmol), A2 (2.87 g, 18.9 mmol) and C2 (0.34 g, 3.14 mmol) in NMP (24.2 g) (1.85 g, 9.43 mmol) and NMP (19.8 g) were added and reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.64 g) and pyridine (4.38 g) were added as an imidization catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (7). The imidization ratio of the polyimide was 60%, the number average molecular weight was 18,500, and the weight average molecular weight was 42,200.

&Lt; Synthesis Example 8 &

D2 (6.63 g, 26.5 mmol), B4 (2.45 g, 4.97 mmol) and Al (4.29 g, 28.2 mmol) were mixed in NMP (24.2 g) and reacted at 80 ° C for 6 hours. 1.30 g, 6.63 mmol) and NMP (19.8 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0% by mass.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.77 g) and pyridine (4.47 g) were added as an imidization catalyst and reacted at 80 ° C for 3.5 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (8). The imidization ratio of the polyimide was 47%, the number average molecular weight was 16,600, and the weight average molecular weight was 38,100.

&Lt; Synthesis Example 9 &

(3.33 g, 21.9 mmol) were mixed in NMP (41.7 g) and reacted at 40 占 폚 for 5 hours to obtain a resin solid content concentration Of 25.0% by mass was obtained.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.74 g) and pyridine (4.45 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (9). The imidization ratio of the polyimide was 62%, the number average molecular weight was 13,900, and the weight average molecular weight was 37,800.

&Lt; Synthesis Example 10 &

A mixture of D3 (7.00 g, 31.2 mmol), B5 (3.53 g, 9.37 mmol), B6 (1.27 g, 6.25 mmol) and A2 (2.38 g, 15.6 mmol) in NMP (42.5 g) C for 5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.62 g) and pyridine (4.36 g) were added as an imidation catalyst and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 占 폚 to obtain a polyimide powder (10). The imidization ratio of the polyimide was 55%, the number average molecular weight was 14,500, and the weight average molecular weight was 34,100.

&Lt; Synthesis Example 11 &

B2 (3.47 g, 8.79 mmol), C2 (0.48 g, 4.44 mmol) and A2 (2.45 g, 16.1 mmol) were mixed in NMP (23.1 g) (2.30 g, 11.7 mmol) and NMP (18.9 g) were added and reacted at 40 ° C for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (6.45 g) and pyridine (3.35 g) were added as imidation catalysts and reacted at 40 ° C for 1.5 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (11). The imidization ratio of the polyimide was 57%, the number average molecular weight was 17,100, and the weight average molecular weight was 39,600.

&Lt; Synthesis Example 12 &

A mixture of D4 (4.36 g, 14.5 mmol), B1 (3.32 g, 8.72 mmol), B6 (1.77 g, 8.71 mmol) and A1 (1.77 g, 11.6 mmol) in NMP (23.2 g) (2.85 g, 14.5 mmol) and NMP (19.0 g) were added and reacted at 40 ° C for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (6.33 g) and pyridine (3.27 g) were added as imidation catalysts and reacted at 40 ° C for 1.5 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain a polyimide powder (12). The imidization ratio of the polyimide was 55%, the number average molecular weight was 18,100, and the weight average molecular weight was 39,500.

&Lt; Synthesis Example 13 &

(2.90 g, 14.8 mmol) and Al (2.25 g, 14.8 mmol) were mixed in NMP (15.5 g) and reacted at 40 ° C for 8 hours to obtain a polyamic acid solution 13 ). This polyamic acid had a number average molecular weight of 18,300 and a weight average molecular weight of 35,500.

&Lt; Synthesis Example 14 &

(5.23 g, 14.0 mmol) and Al (2.13 g, 14.0 mmol) were mixed in NMP (22.9 g) and reacted at 80 ° C for 5 hours. 2.20 g, 11.2 mmol) and NMP (18.7 g) were added and reacted at 40 占 폚 for 6 hours to obtain a polyamic acid solution (14) having a resin solid content concentration of 25.0 mass%. The polyamic acid had a number average molecular weight of 19,500 and a weight average molecular weight of 46,800.

&Lt; Synthesis Example 15 &

The reaction was carried out at 80 ° C for 5 hours, and then the reaction was carried out in the same manner as in Example 1, except that D1 (4.50 g, 18.0 mmol), B1 (5.70 g, 15.0 mmol) 2.35 g, 12.0 mmol) and NMP (19.1 g) were added and reacted at 40 ° C for 5.5 hours to obtain a polyamic acid solution having a resin solid content concentration of 25.0 mass%.

NMP was added to the obtained polyamic acid solution (40.0 g) to dilute to 6 mass%, acetic anhydride (5.40 g) and pyridine (4.18 g) were added as imidation catalysts and reacted at 80 ° C for 3 hours. The reaction solution was poured into methanol (650 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried at 100 ° C under reduced pressure to obtain a polyimide powder (15). The imidization rate of the polyimide was 60%, the number average molecular weight was 16,100, and the weight average molecular weight was 39,800.

Specific polymers of the present invention (polyimide precursor and polyimide) are shown in Table 1.

* 1: Polyamide acid.

&Quot; Synthesis of alkoxysilane monomer represented by formula [A1] of the present invention "

&Lt; Synthesis Example 16 &

&Lt; EMI ID =

Compound (1) (30.0 g), potassium carbonate (25.2 g) and DMF (120 g) were placed in a 500 ml four-necked flask equipped with a magnetic stirrer and allyl bromide (22.1 g) Respectively. Thereafter, the mixture was stirred at 50 占 폚 for 11 hours. The reaction solution was diluted with ethyl acetate (500 g), and the organic phase was washed three times with pure water (200 g). The organic phase was dried over sodium sulfate, filtered and the filtrate was concentrated to dryness to give compound (2) (gain: 34.8 g, gain ratio: 100%).

Compound (2) (20.0 g) and toluene (120 g) were added to a 300 ml four-necked flask equipped with a magnetic stirrer and stirred at room temperature. Next, 700 쨉 l of a Karstedt catalyst (0.1 mol / l xylene solution of platinum (0) -1,1,3,3-tetramethyldisiloxane complex) (700 쨉 l) was added, and trimethoxysilane (12.4 ml ). After stirring at room temperature for 29 hours, the reaction solution was concentrated to dryness to obtain crude product. This was subjected to vacuum distillation and distilled under the conditions of an external temperature of 245 DEG C / pressure of 0.8 torr to obtain an alkoxysilane monomer (A) (gain: 12.2 g, gain ratio: 43%).

&Quot; Synthesis of specific polysiloxane which is component (C) of the present invention "

&Lt; Synthesis Example 17 &

DEME (28.3 g), TEOS (32.5 g), alkoxysilane monomer (A) (4.10 g) obtained in Synthesis Example 16 and MPMS (7.45 g) were placed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube And mixed to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing DEME (14.2 g), water (10.8 g) and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 占 폚 over 30 minutes and further stirred at 25 占 폚 for 30 minutes . Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of methanol solution (1.20 g) having a UPS content of 92% by mass and DEME (0.90 g) was added. After additional 30 minutes at reflux, bangraeng to give polysiloxane solution (1) SiO ₂ in terms of a concentration of 12% by mass.

&Lt; Synthesis Example 18 &

DEEE (32.3 g), TEOS (32.5 g), the alkoxysilane monomer (A) (4.10 g) obtained in Synthesis Example 16 and MPMS (7.45 g) were placed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. And mixed to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing DEEE (14.2 g), water (10.8 g) and oxalic acid (0.70 g) as a catalyst was added dropwise at 25 占 폚 over 30 minutes and further stirred at 25 占 폚 for 30 minutes . Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of a methanol solution (1.20 g) having a UPS content of 92 mass% and DEEE (0.90 g) was added. After further refluxing for 30 minutes, the solution was cooled to obtain a polysiloxane solution (2) having a SiO ₂ concentration of 12% by weight.

&Lt; Synthesis Example 19 &

DEEE (20.4 g), TEOS (20.0 g), the alkoxysilane monomer (A) (8.20 g) obtained in Synthesis Example 16 and MPMS (19.9 g) were placed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube. And mixed to prepare a solution of an alkoxysilane monomer. To this solution, a solution prepared by previously mixing DEEE (12.7 g), water (10.8 g) and oxalic acid (1.10 g) as a catalyst was added dropwise at 25 占 폚 over 30 minutes and further stirred at 25 占 폚 for 30 minutes . Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of a methanol solution (1.20 g) having a UPS content of 92 mass% and DEEE (0.90 g) was added. After further refluxing for 30 minutes, the solution was cooled to obtain a polysiloxane solution (3) having a SiO ₂ concentration of 12% by weight.

&Lt; Synthesis Example 20 &

DEEE (29.2 g), TEOS (38.8 g) and the alkoxysilane monomer (A) (4.10 g) obtained in Synthesis Example 16 were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to obtain an alkoxysilane monomer Was prepared. To this solution, a solution prepared by previously mixing DEEE (14.6 g), water (10.8 g) and oxalic acid (0.50 g) as a catalyst was added dropwise at 25 占 폚 over 30 minutes and further stirred at 25 占 폚 for 30 minutes . Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes. Then, a mixed solution of DEEA (0.90 g) and methanol solution (1.20 g) having a UPS content of 92% by mass previously prepared was added. After additional 30 minutes at reflux, bangraeng to obtain a polysiloxane solution (4) in terms of SiO ₂ concentration of 12% by weight.

&Lt; Synthesis Example 21 &

DEEE (31.6 g) and TEOS (41.7 g) were mixed in a 200 ml four-neck reaction flask equipped with a thermometer and a reflux tube to prepare a solution of an alkoxysilane monomer. A solution prepared by previously mixing DEEE (15.8 g), water (10.8 g) and oxalic acid (0.20 g) as a catalyst was added dropwise to this solution at 25 占 폚 over 30 minutes and further stirred at 25 占 폚 for 30 minutes at room temperature. Then, after heated using an oil bath reflux for 60 minutes, bangraeng to obtain a polysiloxane solution (5) in terms of SiO ₂ concentration of 12% by weight.

The specific polysiloxane (polysiloxane solution) of the present invention is shown in Table 2.

&Quot; Composition of the present invention and production of liquid crystal alignment treatment agent "

In the following Examples 1 to 27 and Comparative Examples 1 to 7, production examples of the composition are described. These compositions are also used for evaluation of a liquid crystal alignment treatment agent.

The composition of the present invention and the liquid crystal alignment treatment agent are shown in Tables 3 to 5.

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " Evaluation of inkjet application property of liquid crystal alignment treatment agent ", " Production of liquid crystal cell ) &Quot;, " liquid crystal orientation property evaluation (normal cell) ", and " production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) ". The conditions are as follows.

&Quot; Printing property evaluation of composition and liquid crystal alignment treatment agent "

The compositions obtained in Examples and Comparative Examples of the present invention were pressure-filtered through a membrane filter having a pore diameter of 1 占 퐉 to perform printing evaluation. As the printing machine, a simple printer S15 type (manufactured by Nihon Photo Printing Co., Ltd.) was used. The printing was carried out on a chromium evaporated substrate cleaned with pure water and IPA (isopropyl alcohol), with a printing area of 80 x 80 mm, a printing pressure of 0.2 mm, five extra substrates, And the drying was carried out on a hot plate at 70 DEG C for 5 minutes.

Then, the resulting resin coating was subjected to pinhole evaluation. The evaluation of the pinhole of the resin coating was carried out by visually observing the resin coating under a sodium lamp. Specifically, the number of pinholes identified on the resin film was counted, and the smaller the number of pinholes, the better the evaluation was.

In addition, the compositions obtained in Examples and Comparative Examples of the present invention can be used for a liquid crystal alignment treatment agent. Therefore, the printability results of the resin coatings obtained in this example and the comparative examples were also referred to as the printability results of the liquid crystal alignment film.

Tables 6 to 8 show the number of pinholes of the resin film (liquid crystal alignment film) obtained in Examples and Comparative Examples.

&Quot; Evaluation of inkjet application properties of composition and liquid crystal alignment treatment agent "

Evaluation of ink-jet applicability was carried out using a solution obtained by pressure filtration of the liquid crystal alignment treatment agent (9) obtained in Example 9 of the present invention and the liquid crystal alignment treatment agent (16) obtained in Example 16 with a membrane filter having a pore diameter of 1 m . For the ink-jet applicator, HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.) was used. The coating was carried out on an ITO (indium tin oxide) -evaporated substrate cleaned with pure water and IPA (isopropyl alcohol) with a coating area of 70 x 70 mm, a nozzle pitch of 0.423 mm, a scan pitch of 0.5 mm, a coating speed of 40 Mm / sec, the time from application to drying was 60 seconds, and drying was carried out on a hot plate at 70 DEG C for 5 minutes.

The pinhole evaluation of the obtained liquid crystal alignment film was performed under the same conditions as " evaluation of printability of composition and liquid crystal alignment treatment agent ".

Tables 6 to 8 show the number of pinholes of the resin film (liquid crystal alignment film) obtained in the examples.

&Quot; Production of liquid crystal cell (ordinary cell) "

A 30 × 40 mm ITO electrode, which was cleaned with pure water and IPA (isopropyl alcohol) using a solution obtained by pressure-filtration of the liquid crystal alignment treatment agent obtained in Examples and Comparative Examples of the present invention through a membrane filter having a pore diameter of 1 μm, The ITO surface of the substrate (40 mm long x 30 mm wide and 0.7 mm thick) was spin-coated on a hot plate at 100 DEG C for 5 minutes and heat-treated at 220 DEG C for 30 minutes in a heat- An ITO substrate with a polyimide liquid crystal alignment film of 100 nm was obtained. The coated surface of the ITO substrate was rubbed with a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm at a roll rotation speed of 1000 rpm, a roll advancing speed of 50 mm / sec, and a pressing amount of 0.1 mm.

Two pieces of the ITO substrates to which the obtained liquid crystal alignment films were attached were prepared, and the liquid crystal alignment film faces were inwardly put together with spacers of 6 탆 in between and a sealant (XN-1500T) (manufactured by Mitsui Chemicals) was printed. Subsequently, the other substrate and the liquid crystal alignment film surface were faced to each other, and the sealant was cured by heat treatment at 150 ° C for 90 minutes in a thermocycling type clean oven to prepare empty cells. The liquid crystal was injected into the empty cell by a low pressure injection method, and the injection port was sealed to obtain a liquid crystal cell (ordinary cell).

The liquid crystal alignment treatment agent (1) to the liquid crystal alignment treatment agent (3) obtained in Examples 1 to 3 and the liquid crystal alignment treatment agent (28) obtained in Comparative Examples 1 to 3, For the cell, a nematic liquid crystal (MLC-2003) (manufactured by Merck Japan) was used as a liquid crystal.

The liquid crystal alignment treatment agents (4) to (8) obtained in Examples 4 to 8, the liquid crystal alignment treatment agents (10) to (15) obtained in Examples 10 to 15, In the liquid crystal cell using the liquid crystal alignment treatment agent (17) to the liquid crystal alignment treatment agent (27) obtained in Example 17 and the liquid crystal alignment treatment agent (31) to the liquid crystal alignment treatment agent (34) obtained in Comparative Examples 4 to 7, Enematic liquid crystal (MLC-6608) (Merck Japan) was used.

&Quot; Liquid crystal orientation property evaluation (normal cell) "

The liquid crystal alignability was evaluated using the liquid crystal cell obtained in the above-mentioned " Production of liquid crystal cell (ordinary cell) ". The liquid crystal alignability was evaluated by observing the liquid crystal cell with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) and confirming presence or absence of alignment defects. Concretely, it was shown that the alignment defect was not observed in the evaluation (excellent in Tables 6 to 8).

Tables 6 to 8 show the results of the liquid crystal alignment properties obtained in Examples and Comparative Examples.

&Quot; Production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) "

The liquid crystal alignment treatment agent 7 obtained in Example 7, the liquid crystal alignment treatment agent 12 obtained in Example 12, the liquid crystal alignment treatment agent 14 obtained in Example 14 and the liquid crystal alignment treatment agent 26 obtained in Example 26 were changed in pore diameter The solution was filtered with a membrane filter of 1 占 퐉 and cleaned with pure water and IPA (isopropyl alcohol). A substrate (40 mm in length × 30 mm in width, 0.7 mm in thickness) having ITO electrodes with a pattern interval of 20 μm at a center of 10 × 10 mm and a substrate with ITO electrodes of 10 × 40 mm at the center 30 mm in width and 0.7 mm in thickness) was spin-coated on a hot plate at 100 DEG C for 5 minutes and at 220 DEG C for 30 minutes in a thermocycling type clean oven to obtain a polyimide coating film having a thickness of 100 nm . After the coated film surface was cleaned with pure water, the substrate was heat-treated at 100 ° C for 15 minutes in a thermocycler type clean oven to obtain a substrate having a liquid crystal alignment film attached thereto.

The substrate to which the liquid crystal alignment film was adhered was assembled with a spacer of 6 mu m interposed therebetween with the liquid crystal alignment film surface on the inner side, and the periphery was bonded with a sealant to prepare empty cells. The polymerizable compound (1) represented by the following formula was dissolved in 100% by mass of a nematic liquid crystal (MLC-6608) in a nematic liquid crystal (MLC-6608) To which a polymerizable compound (1) was added in an amount of 0.3% by mass was injected and the injection port was sealed to obtain a liquid crystal cell.

(108)

A wavelength of 350 nm or less was cut using a metal halide lamp having an illuminance of 60 mW while applying an AC voltage of 5 V to the obtained liquid crystal cell and irradiated with ultraviolet rays of 20 J / cm 2 in terms of 365 nm, (PSA cell) in which the alignment direction of the liquid crystal cell was controlled. The temperature in the irradiator when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.

The response speeds of the liquid crystal cell before and after ultraviolet irradiation were measured. The response speed was measured from T90 to T10 from a transmittance of 90% to a transmittance of 10%.

It was confirmed that the PSA cell obtained in the Examples had a higher response speed of the liquid crystal cell after ultraviolet irradiation than in the liquid crystal cell before the ultraviolet irradiation, so that the alignment direction of the liquid crystal was controlled. It was confirmed that the liquid crystal was uniformly aligned in any of the liquid crystal cells by observation with a polarizing microscope (ECLIPSE E600WPOL) (Nikon Corporation).

&Lt; Example 1 >

DEEA (10.9 g) was added to the polyamic acid solution (1) (12.5 g) having a resin solid content concentration of 10.0% by mass obtained by the synthetic method of Synthesis Example 1, and the mixture was stirred at 25 占 폚 for 1 hour. To this solution, a polysiloxane solution 5 (2.60 g) having a concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 21 was added and stirred at 25 캜 for 2 hours to obtain a composition (1). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (1) was also used for evaluation in the liquid crystal alignment treatment agent (1).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal alignment property (1) Normal cell ").

&Lt; Example 2 >

DEEE (12.4 g) and? -BL (1.51 g) were added to a polyamic acid solution (1) (12.5 g) having a resin solid concentration of 10.0% by mass obtained by the synthetic method of Synthesis Example 1 and stirred at 25 占 폚 for 1 hour Respectively. To this solution, a polysiloxane solution 5 (5.61 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 21 was added and stirred at 25 캜 for 2 hours to obtain a composition (2). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (2) was also used for evaluation in the liquid crystal alignment treatment agent (2).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) ", using the obtained composition (2) and liquid crystal alignment treatment agent Normal cell ").

&Lt; Example 3 >

DEEE (32.3 g) and NMP (4.86 g) were added to the polyimide powder (2) (1.55 g) obtained by the synthetic method of Synthesis Example 2 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (5) (12.9 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 21 was added and stirred at 25 캜 for 2 hours to obtain a composition (3). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (3) was also used for evaluation as the liquid crystal alignment treatment agent (3).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) ", using the obtained composition (3) and liquid crystal alignment treatment agent (3) Normal cell ").

DEEE (12.3 g) was added to polyamic acid solution (3) (14.0 g) having a resin solid concentration of 10.0% by mass obtained by the synthetic method of Synthesis Example 3 and stirred at 25 占 폚 for 1 hour. To this solution, a polysiloxane solution 3 (2.92 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 19 was added and stirred at 25 캜 for 2 hours to obtain a composition (4). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (4) was also used for evaluation in the liquid crystal alignment treatment agent (4).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) " were carried out under the conditions described above by using the obtained composition (4) Normal cell ").

&Lt; Example 5 >

DEEE (10.7 g) and? -BL (2.82 g) were added to polyamic acid solution (3) (9.00 g) having a resin solid concentration of 10.0% by mass obtained by the synthetic method of Synthetic Example 3 and stirred at 25 占 폚 for 1 hour Respectively. To the solution, it was added to the polysiloxane solution (1) (7.50 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 17 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (5). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (5) was also used for evaluation in the liquid crystal alignment treatment agent (5).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (ordinary cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) " were carried out under the above-described conditions using the composition (5) Normal cell ").

&Lt; Example 6 >

DEEE (3.67 g),? -BL (2.70 g) and BCS (5.40 g) were added to a polyamic acid solution (3) (15.5 g) having a resin solid concentration of 10.0% by mass obtained by the synthetic method of Synthetic Example 3, Followed by stirring at 25 ° C for 1 hour. To the solution, a polysiloxane solution 3 was added (1.44 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 19 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (6). No abnormality such as generation of turbidity or precipitates was observed in the composition, and it was confirmed that the solution was a homogeneous solution. The composition (6) was also used for evaluation in the liquid crystal alignment treatment agent (6).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) " were carried out under the above-described conditions using the obtained composition (6) Normal cell ").

&Lt; Example 7 >

DEEE (36.1 g) was added to the polyimide powder (4) (1.70 g) obtained by the synthetic method of Synthetic Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (2) (9.44 g) obtained by the synthetic method of Synthesis Example 18 and having a concentration of 12 mass% in terms of SiO ₂ was added and stirred at 25 캜 for 2 hours to obtain a composition (7). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (7) was also used for evaluation in the liquid crystal alignment treatment agent (7).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", " liquid crystal orientation property evaluation Normal cell ") and " production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) ".

&Lt; Example 8 >

DEEE (24.8 g) and? -BL (8.77 g) were added to the polyimide powder (4) (1.40 g) obtained by the synthetic method of Synthetic Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, was added to the polysiloxane solution (2) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 18 is 12 wt% (11.7 g) and stirred for 2 hours at 25 ℃, to obtain a composition (8). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (8) was also used for evaluation in the liquid crystal alignment treatment agent (8).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property Normal cell ").

&Lt; Example 9 >

DEEE (36.8 g) and? -BL (11.0 g) were added to the polyimide powder (4) (1.00 g) obtained by the synthetic method of Synthetic Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, it was added to Synthesis Example 18 polysiloxane solution (2) in terms of SiO ₂ concentration of 12 mass% (8.33 g) obtained in the synthesis method of, and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (9). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (9) was also used for evaluation in the liquid crystal alignment treatment agent (9).

Using the obtained liquid crystal alignment treatment agent (9), " Evaluation of inkjet application property of liquid crystal alignment treatment agent " was carried out under the above-described conditions.

&Lt; Example 10 >

DEEE (16.1 g),? -BL (4.70 g) and BCS (14.1 g) were added to the polyimide powder (4) (1.35 g) obtained by the synthetic method of Synthetic Example 4 and stirred at 70 ° C for 24 hours to dissolve . To the solution, was added to the polysiloxane solution (4) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 20 is 12 wt% (13.8 g) and stirred for 2 hours at 25 ℃, to obtain a composition (10). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (10) was also used for evaluation as the liquid crystal alignment treatment agent (10).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property ") were carried out under the above- Normal cell ").

&Lt; Example 11 >

DEME (22.3 g), NEP (6.61 g) and BCS (11.0 g) were added to the polyimide powder (5) (2.25 g) obtained by the synthetic method of Synthesis Example 5 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, it was added to the polysiloxane solution (1) (4.69 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 17 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (11). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (11) was also used for evaluation in the liquid crystal alignment treatment agent (11).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal alignment property Normal cell ").

&Lt; Example 12 >

DEEE (25.0 g),? -BL (13.6 g) and BCS (4.53 g) were added to the polyimide powder (5) (2.60 g) obtained in the synthetic method of Synthetic Example 5 and stirred at 70 ° C for 24 hours to dissolve . To this solution, a polysiloxane solution (2) (2.41 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 18 was added and stirred at 25 캜 for 2 hours to obtain a composition (12). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (12) was also used for evaluation in the liquid crystal alignment treatment agent (12).

&Lt; Example 13 >

DEEE (33.6 g) was added to the polyimide powder (6) (1.40 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, was added to the polysiloxane solution (2) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 18 is 12 wt% (11.7 g) and stirred for 2 hours at 25 ℃, to obtain a composition (13). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (13) was also used for evaluation as the liquid crystal alignment treatment agent (13).

&Lt; Example 14 >

DEME (33.2 g) and? -BL (4.11 g) were added to the polyimide powder (6) (2.10 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (1) (4.38 g) having a SiO ₂ -conversion concentration of 12% by mass obtained by the synthetic method of Synthesis Example 17 was added and stirred at 25 캜 for 2 hours to obtain Composition (14). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (14) was also used for evaluation in the liquid crystal alignment treatment agent (14).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", " evaluation of liquid crystal orientation property Normal cell ") and " production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) ".

&Lt; Example 15 >

DEEE (23.2 g), NEP (8.28 g) and BCS (4.14 g) were added to the polyimide powder (6) (1.85 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, it was added to the polysiloxane solution (2) (6.61 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 18 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (15). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (15) was also used for evaluation in the liquid crystal alignment treatment agent (15).

&Lt; Example 16 >

DEEE (26.9 g), NEP (8.67 g) and BCS (4.33 g) were added to the polyimide powder (6) (1.10 g) obtained by the synthetic method of Synthesis Example 6 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, it was added to the polysiloxane solution (2) (3.93 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 18 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (16). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (16) was also used for evaluation in the liquid crystal alignment treatment agent (16).

Using the obtained liquid crystal alignment treatment agent 16, " Evaluation of inkjet application property of liquid crystal alignment treatment agent " was carried out under the above-described conditions.

&Lt; Example 17 >

DEME (20.8 g), NMP (8.23 g) and BCS (8.23 g) were added to the polyimide powder (7) (2.10 g) obtained by the synthetic method of Synthesis Example 7 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (1) (4.38 g) having a SiO ₂ -conversion concentration of 12% by mass obtained by the synthetic method of Synthesis Example 17 was added and stirred at 25 캜 for 2 hours to obtain a composition (17). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (17) was also used for evaluation in the liquid crystal alignment treatment agent (17).

&Lt; Example 18 >

DEEE (37.1 g) and? -BL (4.35 g) were added to the polyimide powder (8) (2.50 g) obtained by the synthetic method of Synthetic Example 8 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution 3 (2.31 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 19 was added and stirred at 25 캜 for 2 hours to obtain a composition (18). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (18) was also used for evaluation in the liquid crystal alignment treatment agent (18).

&Lt; Example 19 >

DEEE (28.6 g),? -BL (2.01 g) and BCS (4.03 g) were added to polyimide powder (8) (1.80 g) obtained in Synthetic Example 8 of Synthetic Example 8 and dissolved by stirring at 70 ° C for 24 hours . To the solution, it was added to the polysiloxane solution (4) (6.43 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 20 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (19). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (19) was also used for evaluation in the liquid crystal alignment treatment agent (19).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) " were carried out under the above- Normal cell ").

&Lt; Example 20 >

DEEE (25.5 g) and? -BL (3.70 g) were added to the polyimide powder (9) (1.30 g) obtained by the synthetic method of Synthesis Example 9 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (2) (8.86 g) having a concentration of 12% by mass in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 18 was added and stirred at 25 占 폚 for 2 hours to obtain a composition (20). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (20) was also used for evaluation as the liquid crystal alignment treatment agent (20).

&Lt; Example 21 >

DEME (21.3 g),? -BL (7.61 g) and BCS (3.80 g) were added to the polyimide powder (9) (1.70 g) obtained by the synthetic method of Synthesis Example 9 and stirred at 70 ° C for 24 hours to dissolve . To the solution, it was added to the polysiloxane solution (1) (6.07 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 17 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (21). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (21) was also used for evaluation in the liquid crystal alignment treatment agent (21).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) " were carried out under the conditions described above by using the obtained composition (21) Normal cell ").

&Lt; Example 22 >

DEEE (24.0 g) and NMP (10.2 g) were added to the polyimide powder (10) (1.70 g) obtained by the synthetic method of Synthesis Example 10 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution 5 (7.63 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 21 was added and stirred at 25 캜 for 2 hours to obtain a composition (22). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (22) was also used for evaluation in the liquid crystal alignment treatment agent (22).

&Lt; Example 23 >

DEEE (32.4 g) and? -BL (4.01 g) were added to the polyimide powder (11) (2.05 g) obtained by the synthetic method of Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (3) (4.27 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 19 was added and stirred at 25 캜 for 2 hours to obtain Composition (23). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (23) was also used for evaluation as the liquid crystal alignment treatment agent (23).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " manufacture of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property) " were carried out under the conditions described above by using the obtained composition (23) Normal cell ").

&Lt; Example 24 >

DEME (30.6 g) and? -BL (4.03 g) were added to the polyimide powder (11) (1.80 g) obtained by the synthetic method of Synthesis Example 11 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, it was added to the polysiloxane solution (1) (6.43 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 17 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (24). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (24) was also used for evaluation in the liquid crystal alignment treatment agent (24).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " manufacture of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property Normal cell ").

&Lt; Example 25 >

DEEE (25.0 g),? -BL (3.83 g) and BCS (7.66 g) were added to the polyimide powder (11) (2.20 g) obtained in Synthetic Example 11 of Synthetic Example 11 and dissolved by stirring at 70 ° C for 24 hours . To the solution, it was added to the polysiloxane solution (2) (2.04 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 18 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (25). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (25) was also used for evaluation in the liquid crystal alignment treatment agent (25).

&Lt; Example 26 >

DEEE (25.0 g) and? -BL (3.76 g) were added to the polyimide powder (12) (1.20 g) obtained by the synthetic method of Synthesis Example 12 and dissolved by stirring at 70 占 폚 for 24 hours. To the solution, was added to the polysiloxane solution (4) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 20 is 12 wt% (10.0 g) and stirred for 2 hours at 25 ℃, to obtain a composition (26). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (26) was also used for the evaluation as the liquid crystal alignment treatment agent (26).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " manufacture of liquid crystal cell (normal cell) ", " liquid crystal orientation property evaluation Normal cell ") and " production of liquid crystal cell and evaluation of liquid crystal orientation property (PSA cell) ".

&Lt; Example 27 >

DEEE (28.4 g),? -BL (2.18 g) and BCS (10.9 g) were added to the polyimide powder (12) (2.50 g) obtained by the synthetic method of Synthesis Example 12 and stirred at 70 占 폚 for 24 hours to dissolve . To this solution was added SiO ₂ obtained by the synthetic method of Synthesis Example 19 The polysiloxane solution 3 (2.31 g) having a converted concentration of 12 mass% was added and stirred at 25 캜 for 2 hours to obtain a composition (27). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (27) was also used for evaluation in the liquid crystal alignment treatment agent (27).

&Lt; Comparative Example 1 &

NMP (29.5 g) was added to polyamic acid solution 13 (8.00 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 13, and the mixture was stirred at 25 占 폚 for 1 hour. To this solution, a polysiloxane solution (5) (4.17 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 21 was added and stirred at 25 캜 for 2 hours to obtain a composition (28). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (28) was also used for evaluation in the liquid crystal alignment treatment agent (28).

Evaluation of printability of composition and liquid crystal alignment treatment agent ", " production of liquid crystal cell (normal cell) ", and " evaluation of liquid crystal orientation property (liquid crystal alignment property evaluation ") were carried out by using the obtained composition 28 and liquid crystal alignment treatment agent 28 under the above- Normal cell ").

&Lt; Comparative Example 2 &

? -BL (29.7 g) was added to polyamic acid solution 13 (8.05 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 13, and the mixture was stirred at 25 占 폚 for 1 hour. To this solution, a polysiloxane solution 5 (4.19 g) having a SiO ₂ concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 21 was added and stirred at 25 캜 for 2 hours to obtain a composition (29). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. This composition (29) was also used for evaluation in the liquid crystal alignment treatment agent (29).

&Lt; Comparative Example 3 &

NMP (17.7 g) and BCS (6.41 g) were added to polyamic acid solution 13 (6.55 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 13 and stirred at 25 占 폚 for 1 hour. To the solution, it was added to the polysiloxane solution (5) (3.41 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 21 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (30). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (30) was also used for the evaluation as the liquid crystal alignment treatment agent (30).

&Lt; Comparative Example 4 &

NMP (29.9 g) was added to polyamic acid solution 14 (8.10 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 14, and the mixture was stirred at 25 占 폚 for 1 hour. To this solution, a polysiloxane solution (3) (4.22 g) obtained by the synthetic method of Synthesis Example 19 and having a concentration of 12 mass% in terms of SiO ₂ was added and stirred at 25 캜 for 2 hours to obtain a composition (31). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (31) was also used for evaluation in the liquid crystal alignment treatment agent (31).

&Lt; Comparative Example 5 &

NMP (21.7 g) and BCS (7.83 g) were added to polyamic acid solution 14 (8.00 g) having a resin solid content concentration of 25.0% by mass obtained by the synthetic method of Synthesis Example 14 and stirred at 25 占 폚 for 1 hour. To the solution, a polysiloxane solution 3 was added (4.17 g) in terms of SiO ₂ concentration obtained in the synthesis method of Synthesis Example 19 12% by weight and the mixture was stirred for 2 hours at 25 ℃, to obtain a composition (32). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (32) was also used for evaluation in the liquid crystal alignment treatment agent (32).

&Lt; Comparative Example 6 >

NMP (36.1 g) was added to the polyimide powder (4) (1.70 g) obtained by the synthetic method of Synthesis Example 4 and dissolved by stirring at 70 占 폚 for 24 hours. To this solution, a polysiloxane solution (2) (9.44 g) having a concentration of 12 mass% in terms of SiO ₂ obtained by the synthetic method of Synthesis Example 18 was added and stirred at 25 캜 for 2 hours to obtain a composition (33). No abnormality such as generation of turbidity or precipitates was observed in this composition, and it was confirmed that the solution was a homogeneous solution. The composition (33) was also used for evaluation as the liquid crystal alignment treatment agent (33).

&Lt; Comparative Example 7 &

DEEE (31.8 g) was added to the polyimide powder (15) (1.50 g) obtained by the synthetic method of Synthesis Example 15 and stirred at 70 占 폚 for 24 hours. Since the dissolution residue of the polyimide powder was seen in the solution, the polyimide powder was stirred at 70 DEG C for 12 hours, but the polyimide powder could not be completely dissolved.

Therefore, the composition (34) and the liquid crystal alignment treatment agent (34) could not be produced.

* 2: Represents the proportion of the polymer in the composition (liquid crystal alignment treatment agent).

* 3: Represents the ratio of the polymer in the composition (liquid crystal alignment treatment agent).

* 4: Represents the proportion of the polymer in the composition (liquid crystal alignment treatment agent).

* 5: Represents the solvent component contained in the polysiloxane solution.

* 6: Since the polyimide powder was not completely dissolved, the composition and the liquid crystal alignment treatment agent could not be adjusted.

* 7: 15 to 24 alignment defects were confirmed.

* 8: 25 or more alignment defects were identified.

As can be seen from the above results, the compositions of the examples of the present invention exhibited uniform coating film properties that did not cause pinholes accompanying cratering when applied to a substrate, as compared with the compositions of the comparative examples. Concretely, the comparison with the composition using the same polyimide precursor or the solvent-soluble polyimide, that is, the comparison between Example 1 and Comparative Example 1, Comparative Example 2 or Comparative Example 3, the comparison between Example 4 and Comparative Example 4, A comparison of Example 5, and a comparison of Example 7 and Comparative Example 6.

The same results were obtained for the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent using the composition of the present invention. Specifically, the liquid crystal alignment treatment agent using the same polyimide precursor or solvent-soluble polyimide, that is, the comparison between Example 1 and Comparative Example 1, Comparative Example 2 or Comparative Example 3, Example 4 and Comparative Example 4 Or a comparison of Comparative Example 5, and a comparison of Example 7 and Comparative Example 6. In particular, even when a liquid crystal alignment treatment agent using a polyimide precursor or a solvent-soluble polyimide obtained by using a diamine compound having a side chain in a diamine component exhibits a uniform coating film property free of pinholes as described above.

Further, in the evaluation of the liquid crystal orientation of the liquid crystal cell, the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the present invention showed no alignment defects accompanying the pinhole as compared with the liquid crystal cell obtained from the liquid crystal alignment treatment agent using the composition of the comparative example , And uniform liquid crystal alignment properties were obtained. Specifically, the liquid crystal alignment treatment agent using the same polyimide precursor or solvent-soluble polyimide, that is, the comparison between Example 1 and Comparative Example 1, Comparative Example 2 or Comparative Example 3, Example 4 and Comparative Example 4 Or a comparison of Comparative Example 5, and a comparison of Example 7 and Comparative Example 6.

Industrial availability

The composition of the present invention can provide a resin coating exhibiting a uniform coating film property without causing pinholes accompanied by cratering when coating the substrate. The same results can also be obtained with a liquid crystal alignment treatment agent using the composition of the present invention.

In addition, the liquid crystal alignment treatment agent of the present invention can obtain a liquid crystal cell in which alignment defects due to pinholes do not occur due to cratering. In particular, the same result can be obtained even when a liquid crystal alignment treatment agent using a polyimide precursor or a solvent-soluble polyimide obtained by using a diamine compound having a side chain as a diamine component.

The liquid crystal alignment treatment agent of the present invention is a liquid crystal display element that performs switching between the transmissive state (also referred to as a transparent state) and the scattered state of liquid crystal, that is, a polymer dispersed liquid crystal (PDLC (Polymer Dispersed Liquid Crystal) And is also useful for a liquid crystal display element using a network liquid crystal (PNLC (Polymer Network Liquid Crystal)).

Particularly, it is useful for a reverse type device which becomes transparent in the voltage unattended state and becomes in the scattering state when voltage is applied. This reverse type device is a liquid crystal display for the purpose of displaying using a glass substrate or a plastic substrate such as PET (polyethylene terephthalate) or an acrylic substrate, and further a dimmer window for controlling the transmission and blocking of light Window), an optical shutter element, a dimmer window of a vehicle such as a car, and a back plate of a transparent display.

Therefore, the liquid crystal display element having the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability and can be suitably used for a large-size, high-definition liquid crystal television or the like and can be used for TN devices, STN devices, TFT liquid crystal devices, And is useful for an alignment type liquid crystal display device.

The liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is also useful for a liquid crystal display element which needs to irradiate ultraviolet rays when manufacturing liquid crystal display elements. That is, a liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes, and a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, A liquid crystal display element manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the electrodes, and further, a liquid crystal layer is provided between a pair of substrates provided with electrodes, A liquid crystal alignment film comprising a polymerizable group polymerizing at least one of an active energy ray and a heat is disposed and a polymerizable group is polymerized while a voltage is applied between the electrodes.

Claims

A composition comprising the following components (A), (B) and (C).
Component (A): a solvent represented by the following formula [1].
[Chemical Formula 1]

(In the formula [1], X ¹ represents an alkyl group having 1 to 4 carbon atoms).
Component (B): at least one polymer selected from a polyimide precursor or a polyimide obtained by reacting a diamine component containing a diamine compound having a carboxyl group and a tetracarboxylic acid dianhydride component.
(C): Polysiloxane obtained by polycondensation of an alkoxysilane containing any one of alkoxysilanes represented by the following formula [A1], formula [A2] or formula [A3].
(2)

Wherein A ¹ is an aliphatic hydrocarbon, a benzene ring, a cyclohexane ring, an organic group having 8 to 35 carbon atoms having a heterocyclic or steroid structure, A ² is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, represents, a ³ is. However, m + n + p is 4, each represents an alkyl group of a carbon number of 1 ~ 5, m is an integer of 1 or 2, n is an integer of 0 to 2, p represents an integer of 0 to 3 to be).
(3)

Wherein B ¹ represents an organic group having 2 to 12 carbon atoms and having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acryl group, a ureide group or a cinnamoyl group, B ² each represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, B ³ each represent an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 or 2, n represents an integer of 0 to 2, Represents an integer of 0 to 3, provided that m + n + p is 4).
[Chemical Formula 4]

The method according to claim 1,
Wherein the component (A) is 50 to 100 mass% of the total solvent contained in the composition.

3. The method according to claim 1 or 2,
Wherein the diamine compound having a carboxyl group as the component (B) is a diamine compound having a structure represented by the following formula [2].
[Chemical Formula 5]

(In the formula [2], a represents an integer of 0 to 4).

3. The method according to claim 1 or 2,
Wherein the diamine compound having a carboxyl group as the component (B) is a diamine compound having a structure represented by the following formula (2a).
[Chemical Formula 6]

The method according to claim 3 or 4,
Wherein the diamine compound having a carboxyl group is 20 mol% to 100 mol% of the total diamines used in the component (B).

6. The method according to any one of claims 1 to 5,
Wherein the diamine component of the component (B) comprises at least one diamine compound selected from the structures represented by the following formula [2b].
(7)

(In the formula [2b], Y represents a structure represented by the following formula [2b-1], formula [2b-2], formula [2b-3], formula [2b-4] m represents an integer of 1 to 4).
[Chemical Formula 8]

7. The method according to any one of claims 1 to 6,
Wherein the tetracarboxylic acid dianhydride component of the component (B) is a compound represented by the following formula [3].
[Chemical Formula 9]

(In the formula [3], Z ¹ is a group of at least one structure selected from the following formulas [3a] to [3j]).
[Chemical formula 10]

8. The method according to any one of claims 1 to 7,
Wherein the alkoxysilane represented by the formula [A2] of the component (C) is at least one selected from the group consisting of allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxy Silane, vinyltris (2-methoxyethoxy) silane, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl acrylate or 3- (trimethoxysilyl) Lt; RTI ID = 0.0 > 1, < / RTI >

8. The method according to any one of claims 1 to 7,
Wherein the alkoxysilane represented by the formula [A2] of the component (C) is at least one member selected from the group consisting of 3-glycidyloxypropyl (dimethoxy) methylsilane, 3- glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxy Propyl trimethoxy silane or 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane.

10. The method according to any one of claims 1 to 9,
Wherein the polysiloxane of the component (C) is a polysiloxane obtained by polycondensation of an alkoxysilane represented by the formula [A1], the formula [A2] and the formula [A3].

11. The method according to any one of claims 1 to 10,
(D), at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and? -Butyrolactone.

12. The method according to any one of claims 1 to 11,
As the component (E), at least one selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Wherein the composition contains at least one solvent selected from the group consisting of propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether.

A resin film obtained from the composition according to any one of claims 1 to 12.

A liquid crystal alignment treatment agent characterized by being obtained from the composition according to any one of claims 1 to 12.

A liquid crystal alignment film obtained by using the liquid crystal alignment treatment agent according to claim 14.

A liquid crystal alignment film obtained by an ink jet method using the liquid crystal alignment treatment agent according to claim 14.

A liquid crystal display element having the liquid crystal alignment layer according to claim 15 or 16.

17. The method according to claim 15 or 16,
A liquid crystal composition comprising a liquid crystal layer between a pair of substrates provided with electrodes and containing a polymerizable compound capable of polymerizing by at least one of active energy rays and heat is disposed between the pair of substrates, Wherein the polymerizable compound is used in a liquid crystal display device manufactured through a process of polymerizing the polymerizable compound while applying a voltage between the polymerizable compound and the polymerizable compound.

A liquid crystal display element having the liquid crystal alignment film according to claim 18.

17. The method according to claim 15 or 16,
A liquid crystal alignment film comprising a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group polymerizable by at least one of active energy rays and heat is disposed between the pair of substrates, Wherein the liquid crystal alignment film is used for a liquid crystal display device manufactured through a process of polymerizing the polymerizable group while applying a voltage.

A liquid crystal display element having the liquid crystal alignment film according to claim 20.